(M. V. Twigg (Auth.), M. V. Twigg (Eds.) ) Mecha PDF

Volume 2
Mechanisms of Inorganic
and Organometallic Reactions
A Continuation Order Plan is available for this series. A continuation order will
bring delivery of each new volume immediately upon publication. Volumes are
billed only upon actual shipment. For further information please contact the
publisher.
Volume 2
Mechanisms of Inorganic
and Organometallic Reactions
Edited by
M. V. Twigg
Imperial Chemical Industries P. L. C.
Billingham, United Kingdom
PLENUM PRESS NEW YORK AND LONDON
Library of Congress Cataloging in Publication Data
Main entry under title:
Mechanisms of inorganic and organometallic reactions.
Includes bibliographical references and index.
1. Chemical reactions. 2. Chemistry, Inorganic. 2. Organometallic compounds. I.
Twigg, M. V.
QD501.M426 1983 541.3'9 83-2140
ISBN-13: 978-1-4612-9659-1 e-ISBN-13: 978-1-4613-2663-2
DOl: 10.1007/978-1-4613-2663-2
1984 Plenum Press, New York
Softcover reprint of the hardcover 1st edition 1984
A Division of Plenum Publishing Corporation
233 Spring Street, New York, N.Y. 10013
All rights reserved
No part of this book may be reproduced, stored in a retrieval system, or transmitted,
in any form or by any means, electronic, mechanical, photocopying, microfilming,
recording, or otherwise, without written permission from the Publisher
Contributors
Dr. f. Burgess Chemistry Department, The University,
Leicester LEl 7RH, U.K.
Dr. R. D. Cannon Chemistry Department, University of East Anglia,
University Plain, Norwich NR47Tl, U.K.
Dr. R. f. Cross Department of Chemistry, The University,
Glasgow G12 8QQ, Scotland, U.K.
Dr. A. f. Deeming Chemistry Department, University College London,
20 Gordon Street, London WCIH OAl, u.K.
Dr. M. Green Chemistry Department, The University, York,
North Yorkshire, YOl 5DD, U.K.
Dr. D. N. Hague Chemical Laboratory, The University, Canterbury,
Kent CT2 7NH, U.K.
Dr. R. W. Hay Department of Chemistry, University of Stirling,
Stirling FK9 4LA, Scotland, U.K.
Dr. M. N. Hughes Chemistry Department, Queen Elizabeth College,
University of London, London W8 7 AH, U.K.
Dr. L. A. P. Kane-Maguire Chemistry Department, Wollongong
University, P.O. Box 1144, Wollongong, N.S.W. 2500, Australia
Dr. A. G. Lappin Chemistry Department, University of Notre
Dame, Notre Dame, Indiana 46556, U.S.A.
vi
Contributors
Dr. P. Moore Department of Chemistry and Molecular Sciences,
University of Warwick, Coventry CV47AL, U.K.
Dr. D. A. Sweigart Department of Chemistry, Brown University,
Providence, Rhode Island 02912, U.S.A.
Dr. C. White Department of Chemistry, The University of Sheffield,
Sheffield S3 7HF, U.K.
Preface
This series provides a continuing critical review of the literature concerned
with mechanistic aspects of inorganic and organometallic reactions in solu-
tion, with coverage over the whole area being complete in each volume.
The format of this second volume is very similar to that of the first, with
material arranged according to reaction type and compound type along
generally accepted lines. Papers discussed are selected on the basis of
relevance to the elucidation of reaction mechanisms but may also include
results of a nonkinetic nature, such as stereochemical studies and product
ratios, when useful mechanistic information can be deduced.
In this volume extra space has been given to areas concerned with
electron transfer processes and substitution reactions of inert complexes,
and to improve convenience for the reader the text has been further divided
to form three additional chapters. Electron transfer processes are discussed
in three chapters: "General and Theoretical," "Reactions between Two
Complexes," and "Metal-Ligand Redox Reactions," while six chapters are
concerned with substitution and related reactions. Here reactions of inert
chromium and cobalt complexes are discussed in separate chapters.
The period of literature coverage is January 1981 through June 1982
inclusive and in a few instances, where delays in delivery of journals have
been encountered, the issues not covered will be included in the next volume.
Similarly, some 1980 references that were not available for inclusion in the
previous volume are discussed here. Numerical results are usually reported
in units used by the original authors, except where data from different
papers are compared and conversion to common units is necessary.
This series was established as a result of demand from members of the
Inorganic Mechanisms Discussion Group (UK), and their continuing sup-
port is appreciated by the contributors, and by others involved in producing
the series. Comments and suggestions regarding this and future volumes
will be welcomed.
vii
Contents
Part 1. Electron Transfer Reactions
Chapter 1. Electron Transfer: General and Theoretical
R. D. Cannon
1.1. Reviews .............. .
1.2. The Marcus-Hush Model . . . . . . . .
1.3. Quantum Effects: (1) The "Normal" Region
1.4. Quantum Effects: (2) The "Inverted" Region
1.5. Optical and Thermal Electron Transfer
1.6. Mixed-Valence Complexes
1. 7. Electron Transfer in the Solid State
Chapter 2. Redox Reactions between Metal Complexes
A. G. Lappin
2.1. Introduction ... .
2.2. Titanium(III) ... .
2.3. Chromium(II) and (III)
2.4. Iron(II) . . . . .
2.5. Cobalt(II)
2.6. Nickel(II) and (III)
2.7. Copper(I) and (II)
2.8. Molybdenum(IV) and (V)
2.9. Ruthenium(II)
2.10. [*Ru(bipyhf+ ....
3
3
6
9
12
16
21
23
23
36
37
42
43
44
45
46
47
ix
x
Contents
2.11. Europium(II) .....
2.12. Miscellaneous Reactions
2.13. Metalloprotein Studies .
Chapter 3. Metal-Ligand Redox Reactions
A. G. Lappin
3.1. Introduction ....
3.2. Ascorbic Acid H2A
3.3. Quinols and Catechols
3.4. Halogens and Pseudohalogens
3.5. Thiols, Sulfur, Selenium, and Tellurium Compounds
3.6. Amines ......... .
3.7. Carbonyls and Carboxylic Acids
3.8. Alcohols and Diols ... .
3.9. Alkenes and Alkyls .... .
3.10. Nitrogen and Nitrogen Oxides .
3.11. Peroxydisulfate and Peroxymonosulfate
3.12. Oxyhalogen Anions
3.13. Reactions of O
2
and H20 2
Part 2. Substitution and Related Reactions
Chapter 4. Reactions of Compounds of the Nonmetallic Elements
M. N. Hughes
4.1. Introduction
4.2. Boron
4.3. Silicon
4.3.1. Silicon Radicals
4.3.2. Base Hydrolysis
4.3.3. Various Substitutions, Isomerizations, and
Redistributions .......... .
4.3.4. Reactions of I3-Substituted Organosilicon
Compounds ............ .
4.3.5. Aqueous Solutions of Silicates
4.4. Nitrogen ......... .
4.4.1. Nitric Acid and Nitration
4.4.2. Nitrogen Dioxide . . .
48
49
49
53
53
55
56
59
61
62
64
65
66
68
70
71
74
79
79
80
80
81
81
83
84
84
84
86
Contents
4.4.3. Nitrous Acid and Nitrosation
4.4.4. Trioxodinitrate and Nitrogen Monoxide
4.4.5. Hyponitrite
4.4.6. Dinitrogen Complexes
4.4.7. Azide
4.4.8. Nitroamine and Hydroxylamine
4.4.9. Hydrazine
4.5. Phosphorus and Arsenic
4.5.1. Phosphorus(V) Compounds
4.5.2. Phosphorus(III) Compounds
4.5.3. Phosphorus(l) Compounds
4.5.4. Arsenic Compounds
4.6. Oxygen
4.7. Sulfur
4.7.1. Oxidation with Peroxo Acids of Sulfur
4.7.2. Reactions of Oxo Acids of Sulfur
4.7.3. Decomposition of a Sulfur Nitroso Compound
(S- Nitrosothiouronium Ion)
4.8. Selenium and Tellurium
4.8.1. Oxidation of Selenium(IV)
4.8.2. Tellurium Compounds
4.9. Halogens
4.9.1. Fluoroxysulfate
4.9.2. Chlorine Compounds
4.9.3. Bromine Dioxide
4.9.4. Iodine Compounds
4.9.5. Oscillating Reactions
4.10. Xenon
Chapter 5. Substitution Reactions of Inert Metal Complexes-
Coordination Numbers 4 and 5
R. J. Cross
5.1. Introduction .............. .
5.2. Substitution at Square-Planar Palladium(II) and
Platinum(II) .............. .
5.2.1. Palladium(II) Complexes
5.2.2. Platinum(II) Complexes . .
5.2.3. Electrophilic Substitutions .
5.3. Ring Opening and Closing Reactions
5.3.2. Platinum(II) Complexes ..
xi
86
89
90
90
90
91
93
93
93
94
95
95
95
97
97
98
98
99
99
99
99
99
100
100
101
101
103
105
106
106
108
111
113
113
115
xii
5.4. Five-Coordinate Species ....... .
5.5. Isomerization of Square-Planar Complexes
5.6. Gold(III) Square-Planar Complexes
5.7. Miscellaneous ..... .
5.7.1. Bridged Complexes
5.7.2. Other Reactions
Coordination Numbers 6 and Above: Chromium
P. Moore
6.1. Introduction
6.2. Aquation and Solvolysis of Chromium(III) Complexes
6.2.1. Unidentate Leaving Groups
6.2.2. Multidentate Leaving Groups
6.2.3. Bridged Dichromium(III) Complexes
6.3. Formation of Chromium(III) Complexes
6.3.1.
Reactions of [Cr(H
2
O)6]3+
6.3.2. Formation of Mixed-Ligand Complexes
6.3.3. Formation of Cr(I1I) Complexes from Cr(II) or
Cr(O)
6.4. Chromium(III) Photochemistry
6.4.1. Ammine Complexes
6.4.2. Amine Complexes
6.4.3. Other Chromium(III) Complexes
6.5. Isomerization and Racemization Reactions
6.6. Base Hydrolysis of Chromium(III) Complexes
6.7. Solids
6.8. Other Chromium Oxidation States
6.8.1. Chromium(II)
6.8.2. Chromium(V)
Coordination Numbers 6 and Above: Cobalt
R. W. Hay
7.1. Aquation . . . . .
7.2. Catalyzed Aquation
7.3. Base Hydrolysis
7.4. Solvolysis
7.5. Anation
Contents
119
122
128
129
129
131
133
133
133
144
144
145
145
145
148
149
149
150
151
151
151
152
152
152
152
153
159
160
165
166
7.6. Solvent Exchange, Racemization, Isomerization, and
Ligand Exchange ....... 168
7.7. JL-Peroxo-dicobalt(l1I) Complexes 170
7.8. Formation .......... 171
7.9. Photochemistry ........ 173
7.10. Reactions of Coordinated Ligands 174
7.10.1. Nitrile Hydrolysis 175
7.10.2. Phosphato Complexes 175
7.10.3. Carbinolamine and Imine Formation 177
7.10.4. Coordinated Azides and Nitriles . . 177
7.10.5. Cobalt-Hydroxide-Promoted Hydrolysis and
Lactonization . . . . . . . . . . . . . 178
7.10.6. Peptide Synthesis ........... 181
7.10.7. Dimethylglyoxime Complexes and B12 Models 182
7.10.8. Base-Catalyzed Exchange Reactions . . . . 184
Coordination Numbers 6 and Above: Other Inert Centers
J. Burgess
8.1. Groups V to VII 187
8.1.1. Vanadium 187
8.1.2. Molybdenum 188
8.1.3. Tungsten 188
8.1.4. Manganese 189
8.1.5. Technetium 189
8.1.6. Rhenium 190
8.2. Iron 190
8.2.1. Pentacyanoferrates(1I) 190
8.2.2. Iron(II)-Diimine Complexes 192
8.2.3. Other Low-Spin Iron(1I) Complexes 197
8.2.4. Iron(III) Complexes 199
8.3. Ruthenium 200
8.3.1. Ruthenium(1I) 200
8.3.2. Ruthenium(III) 202
8.3.3. Ruthenium(III) / (IV) 204
8.4. Osmium 204
8.4.1. Osmium(II) 204
8.4.2. Osmium(IV) 204
8.5. Rhodium 206
8.5.1. Aquation 206
8.5.2. Base Hydrolysis 206
xiv
Contents
8.5.3. Reactions in Liquid Ammonia 206
8.5.4. Catalyzed Aquation 207
8.5.5. Formation 208
8.5.6. Solvent Exchange 208
8.5.7. Ligand Replacement 209
8.5.8. Ring Opening and Closing 209
8.5.9. Photochemistry 209
8.5.10. Oxidation States 2+, 2.5+ 210
8.6. Iridium 210
8.7. Nickel(III) 211
8.8. Platinum(IV) 211
8.8.1. General 211
8.8.2. Inversion at Coordinated Sulfur and Selenium 212
Chapter 9. Substitution Reactions of Labile Metal Complexes
D. N. Hague
9.1. General ..................... 215
9.2. Complex Formation Involving Un substituted Metal Ions:
Unidentate Ligands and Solvent Exchange 216
9.2.1. Bivalent Ions . . . . . . . . . . . . . . .. 216
9.2.2. Ions of Valency 3 and Higher ........ 219
9.3. Complex Formation Involving Un substituted Metal Ions:
Multidentate Ligands 222
9.3.1. Univalent Ions . . . . . . 222
9.3.2. Bivalent Ions . . . . . . . 223
9.3.3. Ions of Valency 3 and Higher 226
9.4. The Effects of Bound Ligands . . . 227
9.4.1. Reactions in Water . . . . 227
9.4.2. Reactions in Nonaqueous Solvents 231
Part 3. Reactions of Organometallic Compounds
Chapter 10. Substitution and Insertion Reactions of Organometallic
Compounds
D. A. Sweigart
10.1. Substitution Reactions
10.1.1. Introduction
237
237
Contents
xv
10.1.2. Carbon Monoxide Replacement in Mononuclear
Metal Complexes . . . . . . . . . . . .. 238
10.1.3. Replacement of Other Ligands in Mononuclear
Metal Complexes . . . . . . . . . . . . 245
10.1.4. Substitution Reactions of Polynuclear Metal
Complexes ....... 252
10.2. Insertion Reactions . . . . . . . . . . . . . 259
10.2.1. Carbon Monoxide Insertion ..... 259
10.2.2. Alkene, Alkyne, and Carbene Insertion 265
10.2.3. Insertion of Other Groups . . . . . . 268
Chapter 11. Metal-Alkyl Bond Formation and Fission; Oxidative
Addition and Reductive Elimination
M. Green
11.1. Introduction 271
11.2. Metal-Alkyl Bonds 272
11.2.1. Chromium 272
11.2.2. R-Co(III)[N
4
] and R-Co(III)[N
2
0
2
] Systems 275
11.2.3. Other Elements ......... 283
11.3. Oxidative Addition and Reductive Elimination 284
11.3.1. Pre transition Metals .... 285
11.3.2. Earlier Transition Metals 285
11.3.3. Cobalt, Rhodium, and Iridium 288
11.3.4. Nickel, Palladium, and Platinum 293
11.3.5. Actinides .......... 300
Chapter 12. Reactivity of Coordinated Hydrocarbons
L. A. P. Kane-Maguire
12.1. Introduction ........... .
12.2. Nucleophilic Addition and Substitution
12.2.1. u-Bonded Hydrocarbons
12.2.2. 7T-Bonded Hydrocarbons
12.3. Electrophilic Attack
12.4. Cycloaddition Reactions . . . . .
301
301
301
303
317
318
xvi
Chapter 13. Rearrangements, Intramolecular Exchanges, and
Isomerizations of Organometallic Compounds
A. J. Deeming
13.1. Mononuclear Compounds
13.1.1. Stereochemical Nonrigidity in Metal Carbonyls
and Their Derivatives
13.1.2. Cis-Trans Isomerism and Exchange in Square
Planar Complexes
13.1.3. Stereochemical Nonrigidity in Five-Coordinate
Compounds
13.1.4. Other Examples of Stereochemical Nonrigidity
13.1.5. Simple Rotation about Metal-Ligand Axes
13.1.6. Ligand Motion Requiring Changes in Hapticity
Contents
319
319
321
322
324
325
329
13.1.7. Metal Migration between Different Ligand Sites . 330
13.1.8. Migrations and Interchanges Involving
Hydrogen Atoms 332
13.1.9. Intraligand Rotations and Rearrangements 336
13.2. Dinuclear Compounds 337
13.2.1. Migration of Carbonyl Ligands 337
13.2.2. Hydrogen Migration Reactions 339
13.2.3. Motion Involving Bridging Organic Ligands 341
13.3. Cluster Compounds 342
13.3.1. Migration of Carbonyl Ligands 342
13.3.2. Hydrogen Migration Reactions 345
13.3.3. Motion Involving Bridging Organic Ligands 345
Chapter 14. Homogeneous Catalysis of Organic Reactions by
Complexes of Metal Ions
C. White
14.1. Introduction . . . . . . . . . . . . . . . . . . .. 351
14.1.1. General Reviews and Elementary Steps in
Homogeneous Catalysis . . . . . . . . .. 351
14.2. Reactions Involving Carbon Monoxide ....... 352
14.2.1. Hydroformylation and Hydrocarboxylation of
Olefins ................. 352
14.2.2. Decarbonylation of Aldehydes . . . . . . . 355
14.2.3. Carbonylation and Homologation of Alcohols,
Halides, and Nitro-Compounds, Ethers,
Carboxylic Acids, and Esters ....... 355
Contents
14.3.
14.4.
14.5.
14.6.
14.7.
14.2.4. Fischer-Tropsch Reactions ..... .
14.2.5. Homogeneous Water-Gas Shift Reaction
(WGSR)
Oxidation
Hydrogenation . . . . . . . . .
14.4.1. Hydrogenation of Alkenes
14.4.2. Hydrogenation of Arenes and Functional Groups
14.4.3. Asymmetric Hydrogenation ..... .
14.4.4. Hydrogen Transfer and Dehydrogenation
Reactions .....
Isomerization Reactions . . . . .
14.5.1. Olefin Isomerization
14.5.2. Skeletal Rearrangements
Alkene and Alkyne Metathesis . .
Oligomerization and Polymerization of Alkenes and
Alkynes ......... .
14.8.
14.7.1. Reactions of Alkenes
14.7.2. Reactions of Alkynes
Reactions of Dinitrogen
References
Author Index
Subject Index
xvii
356
358
359
362
362
363
364
366
368
368
369
370
373
373
375
376
377
423
443
Part 1
Electron Transfer
Reactions
Chapter 1
Electron Transfer:
General and Theoretical
1.1. Reviews
A symposium on radiation chemistry includes short reviews on ion-
molecule reactions, (1) redox properties of free radicals, (2) intramolecular
electron transfer from coordinated ligand radicals(3) and metal ions in
unusual valency states. (4) The increasingly important(S) field of electron
transfer steps in organic reactions has received two reviews. Eberson(6)
examines the applicability of the Marcus and other equations, [see below,
equations (3), (18), and (19)] and by calculating rate constants from theory
comments on the feasibility or otherwise of postulated mechanisms. Chanon
and Tobe(7) have pointed out analogies between substitution reactions
involving electron transfer in organic (aromatic) and inorganic (Pt and Au
complex) systems.
1.2. The Marcus-Hush Model
In this section we review work which lies within what is now accepted
as the classical model of the electron transfer mechanism in solution. We
recall that in this model the second-order rate constant of a general electron
transfer reaction (1) is given by equations (2) and (3). The quantity A = A/4,
A+ +B =A +B+
k = Z exp(-flO*/RT)
flO* = !A(1 + flO*/A)2
(1)
(2)
(3)
3
4 1 General and Theoretical
often called the intrinsic free energy barrier or reorganization energy, is
considered as the sum of inner-sphere and outer-sphere contributions
[equation (4)].
(4)
Calculations of Ao from the electrostatic continuum model and from
quantum mechanical models have been reviewed and compared. (8) The
distinction between electrostatic displacement D and field E is emphasized.
Values of Ao are compared for different physical models of the reacting
molecules, e.g., conducting spheres (the model usually considered in pre-
vious literature) and cavities of various dimensions. In the electrostatic
model a formula for Ao has been given, (9) which applies to any system which
has a symmetrical binuclear structure, and from which Marcus' two-
sphere(lO) and Cannon's ellipsoidal(11) models can be deduced as special
cases.
The two-sphere model gives
e
2
( 1 1 1)( 1 1)
Ao = 47Tco 2
a
1 + 2a2 - R DOD - Ds
(5)
where a 1 and a2 are the radii of the spheres, R is the internuclear distance,
and DOD' Ds are the optical and static "dielectric constants" of the solvent.
Experimentally, the R dependence has been tested using the series of
complexes [(H
3
N)sCo(III)LM(II)(CN)s], with L = imidazolate, pyrazine,
or 4,4'-bipyridyl, and M = Fe or Ru. Values of dG* vary in the expected
way, though the slopes of plots of dG * against R -1 are somewhat less
than predictedY2) The solvent dependence of dG* has been examined
using the reaction [Ru(hfachJ + [Ru(hfac)3r (hfac- = hexafluoroacetyl-
acetonate), and other Ru(III)/Ru(II) systems involving uncharged
reactants. Results agree with equation (5), in contrast to previous
observations, e.g., on [Fe(CsHsht
IO
, which had shown unexpectedly small
changes between solvents.(13) Values of Ao for [Co(NH
3
)6]3+/2+ and
[Co(NH
3
)sFf+
l
+ from electrochemical measurements, are not in accord
with the Marcus prediction. Nonadiabaticity, and deviations from the
continuum model due to short-range solvent structure are considered as
possible reasons for this. (14)
There is growing support for the approximations that, in bimolecular
electron transfer at least, A can be divided into independent contributions
A (A +), A (B) from the two reactants (c.f. an earlier derivation of the Marcus
cross relation on this basis), (15) and moreover that A (A +) = A (A) (cf.
Ref. 16). Using these assumptions, Frese(17) has calculated reorganization
energies for a large number of self-exchange and cross-reactions. In many
cases values of A for individual redox couples are consistent from one
reaction to another. Of interest are the different values of A for
1.2 The Marcus-Hush Model 5
[HFe(CN)6]3- and [Fe(CN)6t-, and the similarity in values for [Fe(CN)6t-
deduced from homogeneous and heterogeneous reactions.
Medium efiects(18) and the relative importance of inner- and outer-
sphere reorganization energy(9) have been assessed for reaction (6). Using
[Co(bipyh]3+ + [Co(terpyh]2+ [Co(bipyh]2+ + [Co(terpyht+ (6)
the conducting-spheres-in-contact model (with assumed radii of 7 A), Ao =
3.3 compared with Ai = 7.9 kcal mol-
1
. The same value of Ao is obtained
for the [Fe(phenh]3+/2+ self-exchange. Overall second-order rate constants
calculated for the two reactions agree with experiment within factors of 2
and 5, respectively.
The long-standing problem of the failure of Marcus theory to correlate
reactions of cobalt(III) complexes, when one of the self-exchange couples
is [Co(H
2
0)6]3+/2+, is considered by Endicott et al.(20) in a comprehensive
review of data on the two reaction series shown in equations (7) and (8)
[Co(NH
3
)6]3+ + B [Co(NH
3
)6]2+ + B+ (7)
[Co(H
2
0)6]3+ + B [Co(H
2
0)6f+ + B+ (8)
where reductants B include aquo ions, macrocycles, and polypyridyl-type
complexes. Both series obey the Marcus equations (when the work terms
are allowed for) except, ironically, the exchange of the hexaaquo complexes
themselves [equation (9)]. For this reaction the rate calculated from the
[Co(H
2
0)6]3+ + [Co(H
2
0)6]2+ = [Co(H
2
0)6]2+ + [Co(H
2
0)6]3+ (9)
correlations is 1O-
12
2 M-
1
S-1; but experimentally 5.0M-
1
S-1. Evidently
the self-exchange is facilitated by some extra pathway which is not available
for the cross-reactions. A water-bridged inner-sphere mechanism is sug-
gested.
A problem in applying the Marcus relationships to organic systems is
that of calculating !J..G e. For some couples the reduction potentials are
unknown and cannot even be precisely defined since the reduced form is
in a repulsive state, e.g., a reduced peroxide (ROORT. Good correlations
have, however, been obtained between log k and a free energy change
!J..G
e
, calculated from the irreversible polarographic reduction wave of the
oxidant. (21) On the other hand, values of the reversible reduction potential
Be may be extracted from irreversible electrokinetic data, by applying the
Marcus equations. This has been done with cyclic voltammetric data using
the dependence of the peak potential on the scan rate. (22) The principle is
analogous to the more familiar use of the Marcus equations to calculate
Be values from a series of homogeneous reactions.(23)
Comparisons of homogeneous and electrochemical rate data continue
to be of interest. In reactions of a series of organometallic compounds with
outer-sphere oxidants (e.g., [Fe(phenh]3+), plots of I1G
t
(electrochemical)
against I1G
t
(homogeneous) are linear with slope 1.0. Values of A increase
with decreasing coordination numbers of the central metal atom, from
Co (CN = 6) through Sn, Pb, and Pt (4) to Hg (2), as expected for increased
participation of the solvent in the transition state. (22)
Inner-sphere reorganization effects are clearly seen in reactions of the
complexes [Co(A
4
)(OH
2
hr+ (A4 = planar macrocyclic tetramine). Only
the Co-O bond lengths change appreciably from the 3 + to the 2 + ion,
and rates of self-exchange correlate with this change.(24)
1.3. Quantum Effects: (1) The "Normal" Region
Quantum effects which have been introduced to refine the original
Marcus model include nonadiabaticity-according to which a reaction is
slowed by a low probability of transfer at the intersection of the energy
surfaces, and nuclear tunneling which tends to increase the rate by allowing
"horizontal" transitions between the surfaces at points other than the
crossing point. Important parameters are the tunneling matrix element Hps>
i.e., the resonance integral between "precursor" and "successor" electronic
configurations (A + ... B) and (A B+) [d. equation (l)t], and the
Franck Condon factors, or vibrational overlap integrals, between reactants'
and products' nuclear configurations.
The nonadiabatic treatment of Hopfield has been elaborated to include
the possibility that Hps may vary with the binding energy or the transferring
electron. Model calculations are given for both optical and thermal electron
transfer (d. below, p. 12) and for barriers of different shapes, including
square energy wells. (25)
Further work on bridged electron transfer includes(26) calculations on
three-atom, symmetrical model systems A-L-A. Using the method of
propagators, time-dependent electron transfer probabilities are calculated
for various energies of the basis orbital of the bridging ligand L. Kuznetsov
and Ulstrup(27) have used perturbation theory to consider the effects of
varying number of bridging atoms, embracing both superexchange and
radical-intermediate electron transfer pathways. Larsson(28) has proposed
rules for predicting relative transfer rates in terms of the occupied and
unoccupied (T and 'IT orbitals. Taking the nonadiabatic model, he calculates
effective interaction matrix elements analogous to the resonance integral
Hps of the two-state approximation.(29)
t Butler has calculated Hps for a number of gas phase reactions such as Ne3+ + H ...... Ne
2
+ +
H+.(92) For reviews dealing with gas phase electron transfer see Refs. 93 and 94.
1.3 Quantum Effects: (1) The "Normal" Region 7
The main emphasis however of work reported in the period under
review has been on comparisons between theory and experiment, especially
on the difficult question of whether any of the familiar inorganic reactions
are significantly non adiabatic or not. Zawacky and Taube(30) have measured
intramolecular electron transfer rates in complexes of the type
[(H3NhCoLRu(II}(NH3}4X], where the bridging groups include isomeric
carboxypyridines. With X = H
2
0, rates are not very sensitive to the nature
of L, and the reactions are thought to be close to the adiabatic limit; with
X = [S03f- however, rates are substantially less. This suggests that the
[S03f- group, a 7T-electron acceptor, decreases the electronic coupling,
which is "tantamount to admitting that electron transfer is strongly non-
adiabatic." (On coupling through bridging units, see also section 1.6 below).
Brunschwig et al.(31) have reviewed existing non adiabatic theories for
comparison with data on bimolecular reactions. They define the "semi-
classical" rate constant ksc by equation (10) where kcl is the "classical"
(10)
rate constant k of equation (2), Kel expresses the nonadiabaticity effect,
and r n expresses the nuclear tunneling. A full quantum mechanical treat-
ment considers the electron transfer as a radiation less transition and
averages the probabilities Wpv for transfer from each vibronic level v of
the initial or precursor state p, to each level w of the final or successor
state s, using the Fermi Golden Rule [equation (11)] where (xpvIXsu) is the
Wpv = (47T
2
H;s/h)pw
Pw = Iw l<XpvlxswW8(Bpv - Bsw)
(11)
(12)
vibrational overlap integral, the e are vibronic energies, and the 8 function
ensures conservation of energy. Brunschwig et al. calculate rate constants
ksc within this semiclassical formalism in excellent agreement with those
from a full quantum mechanical treatment. For reaction (13) they assess
[Fe(H
2
0)6]3+ + [Fe(H
2
0}6]2+ -. [Fe(H
2
0}6]2+ + [Fe(H
2
0)6]3+ (13)
the contributions from the various initial-state vibronic levels, at certain
temperatures, and plot activation parameters versus temperature.
Nevertheless, an attempt to decide the degree of nonadiabaticity of this
reaction is inconclusive owing to uncertainty in the values of the metal-
oxygen distances (see below, p. 8).
Reaction (13) is treated in more detail by Newton.(32) Calculations of
ligand-to-metal charge transfer confirm that the transferring electron is
effectively localized on the metal atoms. The integral Hps is calculated for
various distances and relative orientations of the two Fe06 octahedra, and
rate constants are calculated within a factor of 2 of the experimental values.
The entropy or enthalpy contributions are "clear manifestations" of both
nonadiabatic behavior and nuclear tunneling, but the most remarkable
conclusion is that the bulk of the electron transfer occurs at metal-metal
distances substantially less than the usually accepted contact distance of
6.9 A. It is suggested that in the reacting pair, a vertex of one octahedron
pokes into a face of the other. Further calculations with more detailed
treatment of the interaction forces between the two ions imply distances
as short as 4.5 A. The results are supported by a successful calculation of
the rate of the analogous nuclear spin relaxation reaction (14) where the
(14)
indices m and m' show a change of spin states induced by collision with
the paramagnetic Ni
2
+ ion, and of the ionic strength dependence of reaction
(15). Siders and Marcus(33) have also calculated quantum effects on reaction
(15)
(13), and on the self-exchange reactions [Co(NH
3
)6]3+/2+ and
[Ru(NH
3
)6]3+/2+. Franck-Condon factors are treated by the Golden Rule,
and the solvent is introduced as a harmonic oscillator, but with two frequen-
cies instead of one as in most earlier treatments. This refinement is expressed
in the continuum model by introducing a dielectric constant D ir for the
infrared frequency region in addition to Ds and Dop of equation (5). These
authors likewise conclude that tunneling and nonadiabaticity are significant
though not large. In reaction (13), with one set of calculations, other things
being equal, inclusion of tunneling effects raises the rate constant by a factor
of 3.5. In the system [Ru(NH
3
)6]3+/2+,o4) quantum effects are negligible,
while in [Co(NH
3
)6]3+/2+ (33,34) they are again appreciable but not large,
nuclear tunneling enhancing the rate by a factor of about 7.(34) The major
difference in rates between these two systems-experimentally the ratio is
more than 10
15
-is attributed to reorganization energy differences. (33)
All attempts to calculate absolute values of rate constants depend on
precise knowledge of the difference of the metal-ligand distances in the
oxidized and reduced forms of the complexes. For exchange between
octahedral complexes, such as reaction (13), Sutin(35) obtained them via
equations (16) and (17), where r2, r3 are metal-ligand distances in the Fe
2
+
* 2r2r3
r =--
r2 + r3
(16)
(17)
1.4 Quantum Effects: (2) The "Inverted" Region 9
and Fe
3
+ complexes, and r* is the value adopted by both complexes in the
transition state. Values of r2, r3 have hitherto been known only for the
solid state,t but now, from X-ray scattering and EXAFS data, they are
becoming available for complexes in solution. For a number of hydrated
transition metal ions, the distances in solution turn out to be smaller than
in the crystal, (36) and the differences (r2 - r3) vary as well. For
[Fe(H
2
0)6]3+/2+, we now have (r2 - r3) = 0.105 A (solution, EXAFS),
0.12 A (solution, X-ray), 0.14 A (solid). The changes from solid to solution
are enough to change significantly conclusions on the importance of adiaba-
ticity of tunneling effects mentioned above.(31),*
Also significant are the two differences (r2 - r*) and (r* - r3). If these
do not exceed the amplitudes of the metal-ligand vibrations, there will be
no activation energy requirement at all in the classical sense, Le., no
substantial transfer of energy from modes other than the breathing modes
of the two complexes. For the Fe(H
2
0)2+ system Irn - r*1 are sufficiently
large to require activation, and the new data from solution do not
change this conclusion.(31) For the system [Mn04r12-, however, the latest
Irn - r*1 values only just exceed the amplitude and the calculated Ai is only
1.6 kcal mol-
l
.(37)
The deuterium isotope effect has been proposed as another experi-
mental probe for quantum effects. Model calculations on systems such as
[Co(NH
3
)6]3+/2+ indicate that the main effects on replacing H by Dare
due to inner-sphere reorganization, and that the effect should become very
large at low temperatures. The small values of kH/ kD actually observed so
far tend to confirm that quantum effects are not very significant at room
temperature. (38)
1.4. Quantum Effects: (2) The "Inverted" Region
The Marcus equation (3) (above) predicts that when 6.G
8
is more
negative than -A, a further decrease causes 6.G
t
to rise: the rate becomes
slower although the driving force is increased. A growing body of data
indicate that this either does not happen or if the rate does become slower
in this "inverted" or highly "exergonic" region, it does not follow the
t Of interest in this connection is an ab initio calculation of the Fe
2
+ -OH2 and Fe
3
+ -OH2
bond lengths. Results are given for hypothetical complexes [Fe(OH
2
)mr+ with m = 1-6,
and the latter are in good agreement with the crystal structural values. (95)
t Further X -ray structural data of interest for electron transfer studies include [FeCI
6
]3- and
[FeCI
6
]2- ions, (96) and Cu(I) and Cu(II) complexes with similar tridentate N-S-N ligands. (97)
See also footnote on p. 16.
simple dependence implied by equation (3). t The commonest situation
appears to be that with decreasing t:..G
e
the rate increases to the diffusion-
controlled limit, and then remains at that limit. Empirical equations have
been proposed by Rehm and Weller(39) [for electron transfer, equation
(18)], and by Marcus(40) and Agmon and Levine(41) [for atom transfert
equation (19)] both having the features that t:..G*- 0 as t:..G
e
- -00;
and, again in contrast to equation (3), t:..G* --+ t:..G
e
as t:..G
e
--+ +00.
t:..G* = !t:..G
e
+ {(!t:..G
e
)2 + A 2}1/2
t:..G* = t:..G
e
+!A In{1 + exp[(t:..G
e
fA) In 2]}
(18)
(19)
Equation (18) has been used in a further recent paper on electron transfer
reactions of excited organic species, (42) and the leveling of log k at highly
negative t:..G
e
is found also in electron transfers from neutral molecules
to acceptors such as trapped holes in glasses.(43,44) [Plots of log k rather
than t:..G* against t:..G
e
are now generally preferred, in view of the non-
applicability of equation (2) to nonadiabatic reactions.]
In an extensive review of metal-metal electron transfer reactions
Balzani et al. (45) have argued that data in the highly exergonic region are
a good criterion of nonadiabaticity. In the log k-t:..G
e
plots, strongly
non adiabatic reactions will have a low plateau, while the main effect of a
change in reorganization energy is to change the value of !1G e at which
the onset of the plateau occurs. It is found that data for reactions of
[Ru(NH
3
)6]"+ and [Fe(H
2
0)6]"+ can be fitted to curves of the type of
equation (19), using average A values of 10.6 and 17.4 kcal mol-t, respec-
tively, but for Eu:: more complicated curves are obtained, which are
viewed as having a lower plateau, followed by a change to a higher one,
indicating a different reaction path at t:..G
e
:c:: 1 eV. The nonadiabaticity
factor [Kel of equation (10)] for the Eu3+12+ couple is estimated as _10-
5
,
A series of reactions involving excited aromatic molecules exhibits a very
clear double plateau consistent with nonadiabaticity in the range t:..G e >
-1.5 e V and a change to another more efficient reaction path at t:..G e <
-1.8 eV.(46)
t Marcus and Siders(51) point out that the familiar maximum in the charge transfer absorption
spectrum has the same physical origin as the predicted maximum in a plot of logk against
I:J.G e; also in the field of radiationless transitions the effect of decreasing rate with increasing
exothermicity is well established and is known as the "energy gap law" (Marcus, Ref. 52,
citing Ref. 98).
* Marcus(52) emphasizes that although equation (19) has a theoretical basis for atom transfer
reactions, when applied to electron transfer reactions it is purely empirical "and has no
advantage over the frankly empirical Rehm-Weller equation," i.e., equation (18); d. Ref. 45,
note 22.
1.4 Quantum Effects: (2) The "Inverted" Region 11
(20)
Reactions of the type (20) which feature in the quenching of excited
[RuLtf+(L = bipy or phen) by molecules Q such as methylviologen cation,
are highly exergonic, with tlOB around -2 eV. Rates, however, increase
d
. h . . I . "ce (47) Th
slightly rather than ecrease, WIt Increasmg y negative Q ,ese
data recall the earlier work from the same laboratory(48.49) in which reactions
of the type in equation (21) were studied with Q = Ru(II) and Os(1I)
(21)
complexes, and in which k decreases with increasingly negative tlO
B
, but
not to the extent predicted by equations (2) and (3). Marcus and Siders(50)
have discussed these data in the light of modified Marcus treatments which
take account of nuclear tunneling, but they conclude that these theories
too are inadequate to explain the results. They suggest alternative reaction
paths leading to excited-state products, so that tlOBis not in fact as negative
as had been assumed.
Another possibility(50) which can explain nonabnormal behavior (so
to speak) is that electron transfer may take place over longer distances in
the inverted region than in the normal region. Qualitatively, the effect of
increasing R is to increase the reorganizational energy barrier A [equation
(5)] and in the inverted region, this increases the rate [equations (3) and
(4)], though on the other hand, if the reaction becomes non adiabatic, as it
presumably m:lst if the distance is great enough, further increase of distance
will markedly decrease the rate. These considerations are treated in more
detail in another paper.(54) Plots of predicted log k against tlOB are given,
using diffusion theory, nonadiabaticity, and R -dependent reorganization
energies calculated electrostatically. Even with this theory, however, the
Creutz-Sutin data are only fitted when excited-state products are assumed.
Inclusion of variable electron transfer distance can also raise the frequency
factor Z [equation (2)] by a factor of about 10 and this too improves the
fit of the data. (52),t
The possibility of circumventing the effects of diffusion has been
pointed out. (54) If one of the reagents in the electron transfer process is
generated in situ by pulse radiolysis, as in reaction (22) at the moment of
B + hv ..... B* (22)
excitation species A + and B* are randomly distributed, but when the
reaction (23) proceeds, the distribution changes and the short-distance
(23)
t Electron transfer over varying distances features also in a recent discussion of the
photodiffusion of trapped electrons. (99)
pairs are depleted more rapidly, until a steady state is reached. It is this
steady state which is measured in conventional kinetics. The initial rate,
however, is closer to the true electron transfer rate. The theory of this
effect is given by Marcus and Siders, and curves of log k versus I:J.O
8
are
plotted for rate constants k measured at different times after the excitation.
The opposite extreme condition of equation (3) is highly endergonic
electron transfer (Ll0
8
;:;: A). This is found(47) in reactions of the type in
equation (24) where L = diamines of the bipyridyl type. Actual values of
[RuLf]2+ + [RhL
3
]3+ ....... [RuL
3
]3+ + [RhL
3
f+ (24)
Ll0
8
are not known but rates decrease with increasingly negative
E
8
(Ru(III)/*Ru(II)) and the slope of a plot of log k versus E8 is close to
the value 16.9 V-I expected from equations (18) and (19), or from the
Marcus equation (3) with I:J.0
8
::::: A. The equation actually used to fit the
data was the Marcus equation. For the two couples RuLj+ /*RuLi+ and
RhL
3
+/
2
+ an average self-exchange rate constant was obtained as 2 x
10
9
M-
1
S-I.
1.5. Optical and Thermal Electron Transfer
Interest continues in the problem of relating the optical electron
transfer process (25) to the corresponding thermal process [equation (26)].
+ hv +
A ". B ----. (A". B )* (25)
In these equations the centers A and B are presumed to be linked so that
reaction (26) is intramolecular. When the available thermal reaction is
A
+ ket A +
" . B ----. " . B (26)
bimolecular [equation (1)] there is the problem of calculating a precursor
complex formation constant Kip [equation (27)]. The Marcus-Hush model
A + + B A + .. B, Kip (27)
applied(53) to the processes (25) and (26) leads to equations (28)-(30) where
ii
max
is the wave number and emax the extinction coefficient of the absorption
Eth = 4 (Eop - E th)
ket = lIet exp( -Eth/ RT)
lI
e
t = 9.76 x 1010(iimax)1/2emaxI:J.1I1/2/r2
(28)
(29)
(30)
maximum in the intervalence charge transfer (IT) spectrum, Eop = hciimax,
Ll1I1/2 is the IT bandwidth, and r is the internuclear distance A-B. To test
1.5 Optical and Thermal Electron Transfer 13
these equations Oliveira and Haim
(53
) have determined the rate constant
of reaction (31) in which My
2
+ = methylviologen cation. The observed
My2+ + [Fe(CN)6t- ...... MY+ + [Fe(CN)6]3- (31)
value k = 2.4 X 10-
5
M-
1
S-l is quite close to the value calculated from
optical data, k = (2-3) X 10-
4
M-
1
s-\ but it is considered that the agree-
ment is fortuitous, since the rate-determining process is not electron transfer
but dissociation of the successor complex, i.e., step 3 in the sequence (32).
Reviewing this and two other reactions on the basis of revised calculations
I
My2+ + [Fe(CN)6]4- My
2
+ . [Fe(CN)6t-
-1
* MY+ + [Fe(CN)6]3- (32)
using equations (28)-(30) the authors argue that the agreement between
optical and thermal data is not satisfactory.
Further examples of optical electron transfer processes are listed in
Table 1.1. In some cases(54,55) when reaction(26) is not spontaneous, irradi-
ation in the IT band leads to net oxidation-reduction reactions. In the
reactions [Co(III)(NH
3
)sLr+ + [Fe(CN)6t-, thermal electron transfer
rates are found to vary little over a series from L = pyridine to L =
1 ,2-di( 4-pyridyl)ethene. It is considered that the reactions involve the
approach of the Fe complex to the ammonia side of the cobalt, and that
they are adiabatic.
Fluorescence intensity measurements(56) on the system [Os(5CI-
phenhf+ + [Fe(CN)6t- have been obtained. Rates calculated from the
Marcus equation, using experimentally measured B8 values, are in quite
good agreement. In the corresponding system with [*Ru(bipYhf+ as oxi-
dant, the electron transfer reaction is considered to be diffusion controlled.
Irradiation of the complex (1) leads to a detectable nonradiative decay
process which is interpreted as shown in Scheme 1 where S2 =
C6H5SCH2CH2SC6H5; B = 2,2'-dipyridyl; L = 4,4'-bipyridyl and related
ligands. The slow step is electron transfer from the bridging to a non bridging
Scheme 1
[S4CIRu(II)(L)Ru(III)CIB2r [S4C1Ru(III)(L -)Ru(III)CIB
2
]3+
fk 1
[S4C1Ru(III)(L)Ru(II)CI(Bhr (-- [S4C1Ru(III)(L)Ru(III)CI(B-)Br
T
a
b
l
e

1
.
1
.

O
p
t
i
c
a
l

a
n
d

T
h
e
r
m
a
l

E
l
e
c
t
r
o
n

T
r
a
n
s
f
e
r

D
a
t
a

I
T

a
b
s
o
r
p
t
i
o
n

b
a
n
d

F
o
r
m
a
t
i
o
n

C
o
m
p
l
e
x

c
o
n
s
t
a
n
t

I
I
m
a
x
,

e
,

E
'
h

k
e

(
o
b
s
)
,

A
+

.
.
.

B

K
a
,
M
-
1

1
0
3

e
m
-
I

M
-
1
c
m
-
1

k
c
a
l

m
o
l
-
I

-
I

s

[
R
u
(
I
I
I
)
(
N
H
3
l
s
C
I
]
2
+

.

[
R
u
(
I
I
)
(
C
N
)
6
t
-
2
1
6

1
9
.
6

2
0

[
(
H
3
N
)
5
R
u
(
I
I
I
)
N
C
R
u
(
I
I
)
(
C
N
)
5
r

1
4
.
7

2
8
0
0

[
R
u
(
I
I
I
)
(
C
N
)
6
]
3
-
[
R
u
(
I
I
)
(
N
H
3
)
5
C
I
+
]

>
1
0
5

2
7
.
8

6
0
0

>
1
0
3

2
.
4

x

1
0
3

2
2
.
5

1
6
0

1
.
5

x

1
0
-
2

[
C
o
(
I
1
I
)
(
N
H
3
)
5
L

3
.
2

x

1
0
3

2
1
.
3

2
4
0

4
.
7

x

1
0
-
2

2
.
5

x

1
0
3
i

1
1
.
0

3
3

[
R
u
(
I
I
I
)
(
N
H
3
)
5
p
l
+
]
[
R
u
(
C
N
)
:
-
]

2
.
7

x

1
0
3
i

1
5
.
5
5

3
8

[
R
u
(
I
I
I
)
(
N
H
3
)
5
P
y
3
+
]
[
O
s
(
C
N
)
:
-
]

2
.
9

x

1
0
3
i

1
5
.
2

4
0

F
e
2
(
I
I
I
)
F
e
(
I
I
)
O
(
O
O
C
C
H
3
)
6
(
H
2
O
h

1
3
.
8

1
.
2
0

F
e
2
(
I
I
I
)
F
e
(
I
I
)
O
(
O
O
C
C
H
3
)
6
(
p
y
h

0
.
4
3

C
y
t
o
c
h
r
o
m
e

c
/
F
e
(
C
N
)
6

m

[
(
H
3
N
)
5
R
u
(
I
I
I
)
N
C
C
4
H
5
F
e
(
I
I
)
(
C
5
H
5
)
t
+

9
.
0
9

3
8
0

k
e

(
c
a
l
e
b
)
,

S
-
I

R
e
f
.

5
4

5
4

(
e
f
.

1
0
7
)

5
4

5
5

1
0
8

1
0
8

1
0
9

1
0
9

1
0
9

8
3

8
3

1
1
2

1
1
6

.
.
.
.
.
.

-
I
:
>
.
.

.
.
.
.
.
.

;
:
s

'
"

;
:
s

$
:
:
0
.
.

'
"

<
:
:
>

[
(
H
3
N
)
s
R
u
(
I
I
)
N
C
C
H
:
C
H
C
4
H
s
F
e
(
I
I
)
(
C
s
H
s
)
]
3
+

2
2
0
'

M
y
2
+

+

2
.
4

X

1
0
3
e

[
(
N
H
3
)
s
R
u
p
z
R
u
(
e
d
t
a
)
f

y
V

.
.
.

y
I
V
I

a

F
o
r
m
a
t
i
o
n

c
o
n
s
t
a
n
t

f
o
r

i
o
n

p
a
i
r
,

A
+

+

B

A
+

.
.
.

B

b

F
r
o
m

o
p
t
i
c
a
l

d
a
t
a
,

s
e
e

t
e
x
t
.

,

R
e
f
e
r
e
n
c
e

1
1
3
.

8
.
7
5

3
3
0

1
0
.
9
1

4
0

7
.
1

6
9

6
.
6

7
2

3
.
9

1
3
.
2

0
.
1
4

d

R
e
v
i
s
i
o
n

o
f

e
a
r
l
i
e
r

a
u
t
h
o
r
s
'

c
a
l
c
u
l
a
t
i
o
n

(
R
e
f
.

1
1
7
)
,

u
s
i
n
g

v
.
,

f
r
o
m

e
q
u
a
t
i
o
n

(
3
0
)

i
n

p
l
a
c
e

o
f

R
T
/
L
h
.

,

A
s
s
u
m
e
d
.

1
.
7

x

1
0
-
4

1
.
6

x

1
O
-
2
f

1
.
8

x

1
0
3

8

x

1
0
9

1
.
9

x

1
0
1
0

f

S
e
c
o
n
d
-
o
r
d
e
r

r
a
t
e

c
o
n
s
t
a
n
t

(
M
-
I

S
-
I
)

f
r
o
m

a
p
p
l
i
c
a
t
i
o
n

o
f

t
h
e

M
a
r
c
u
s

c
r
o
s
s

r
e
l
a
t
i
o
n
.

,

S
e
c
o
n
d
-
o
r
d
e
r

r
a
t
e

c
o
n
s
t
a
n
t

(
M

1

s

'
)
.

h

D
a
t
a

f
o
r

s
u
b
s
t
i
t
u
t
e
d

p
y

d
e
r
i
v
a
t
i
v
e

a
l
s
o

r
e
p
o
r
t
e
d
;

E
o
p

c
o
r
r
e
l
a
t
e
s

w
i
t
h

t
l
.
H
8

f
o
r

t
h
e

t
h
e
r
m
a
l

e
l
e
c
t
r
o
n

t
r
a
n
s
f
e
r

r
e
a
c
t
i
o
n
.

,

2
3
C
,

0
.
1

M

N
a
O
A
c

(
H
O
A
c

b
u
f
f
e
r
)
.

I

P
o
l
y
v
a
n
a
d
i
c

a
c
i
d

g
e
l
.

m

A

p
r
e
v
i
o
u
s
l
y

r
e
p
o
r
t
e
d

I
T

b
a
n
d

i
s

n
o
t

c
o
n
f
i
r
m
e
d
.

1
1
6

5
3

1
.
9

X

1
0

-
5
g

5
3

2
.
3

X

1
0
6
d

5
3

1
.
9

X

1
0
1
2
d

1
0
7

(
e
f
.

5
3
)

5
6

8
0

8
1

.
.
.
.
.

e
.
.

;
:
:

l
:
>
.
.
.

'
"

e
.
.

<
"
>

;
:
:

;
:
:

'
"

.
.
.
.

.
.
.
.
.

v
,

ligand, and the final metal-to-metal electron transfer is too rapid to fol-
low. (57) Its rate constant has been estimated(58) as k - 6 X 10
10
S -1.
The comparison of thermal electron transfer data with optical data
from photoelectron experiments is explored by Delahay.(59.60) Reorganiz-
ation energies derived from the process (33) are compared with those from
(33)
thermal exchange reactions. Agreement is close in some cases (A = Fe
z
+,
Mnz+, Co
z
+), but in other cases the optical values are about 0.3 eV below
the thermal(59) (cf. Ref. 61).
1.6. Mixed-Valence Complexesf
A review by Wong and Schatz(6Z) consolidates earlier work on the
Piepho-Krausz-Schatz (PKS) vibronic coupling model, comparing this
model with the Marcus-Hush and the various nonadiabatic models. The
article, which is a model of clarity, relates the ground state properties of
mixed-valence systems (localized versus delocalized cases), the optical
properties (position and shape of the IT band), and the thermal electron
transfer properties (rate and temperature dependence of activation energy)
to two critical parameters'\ and e which correspond to the reorganization
energy and the tunneling integral of the Marcus and semiclassical models.
Lindenberg and Ratner have discussed the question of localized versus
delocalized valency states by using a four-site model. In the simplest case,
this is the system Hz' .. Hr, in which the two H-H distances can be varied
to provide different values of the coupling parameter. The criteria for
valence trapping, and rates of intramolecular electron transfer are discussed
in terms of the model. (63)
The Creutz-Taube(64) ion (2, L = pyrazine) and related systems con-
tinue to be of interest. Wong and Schatz(6Z) conclude that it is a class III
[(H
3
N)sRuLRu(NH
3
)s]s+
2
t Some other mixed-valence systems of special interest for electron transfer studies include
the ion [Y 10026]"'- containing ylV 05 and yV 0
4
units, (100) [Cr30(00CCF3)6(Pyh] contain-
ing indistinguishable Cr(III) and Cr(II),(lOl) [PtBr2(NH3h][PtBr4(NH3h] (a redetermi-
nation of structure(102); spectral and electrochemical data on [Cu(III)Cu(II)Cu(II)OL
3
]2+
(L = isonitroso ketimine(103,104); [Ni(TBP)h[Ni(TBP)tI3" which is a doubly mixed
valent, with metallic conductivity and rapid interconversion between [Ni(II)(TBP+)] and
[Ni(III)(TBP)] tautomers (TBp
2
- = tetrabenzoporphyrinate(lOS); Pt(II) doped in
K
2
Pt(CN)6 (spectra)(llO); [ptX
6
]2- and [ptX
4
]2- doped in Cs
2
ZrX
6
(X = Cl or Br:
spectra(lll).
1.6 Mixed- Valence Complexes 17
compound in the Robin and Day(6S) sense but very close to the class II-III
boundary. A problem remains however: the observed intervalence band
is markedly unsymmetric and the best fit of the shape to the equations of
the PKS theory implies a very slight degree of valence trapping. That is,
the probability distribution P(q) of the normal coordinate q which carries
the electron transfer has two slight maxima rather than one. The PKS
theory thus still predicts far-infrared tunneling transitions due to the
degeneracy of the wave function. These have been searched for, (66) and
not found. Krausz et al. propose that the complex is wholly delocalized,
and that the assymmetry of the absorption band must have some other
origin. Wong and Schatz(62) now suggest that the observed band is in fact
a superimposition of two IT bands.
In a different approach to the Creutz-Taube ion, (67) structural data
for [Ru(NH
3
)s(pyz)]3+ and [Ru(NH
3
)s(pYZ)]2+ have been used to predict
the properties of the hypothetical localized -valence complex
[(NH
3
)sRu(III)(pyz)Ru(II)(NH
3
)s]5+. The delocalization energy is thus
estimated to be 0.4 eV, while the barrier to delocalization in the crystal
state is only 0.2 eV, giving a class III, or average-valency structure. In
aqueous solution the delocalization barrier is greater, but the ion remains
in class III, though close to the borderline with class II.
Tanner and Ludi(68) have extended the PKS calculations to a series of
18 Ru(III)-Ru(II) dimers, calculating the parameters of the model by fitting
the shapes of the IT bands. They confirm the delocalized character of the
complexes 2 with e.g., L = NCCN, NCCHCN-, and the progressively
weaker coupling along a series such as L = pyz, 4,4'-bipy, CH
2
(C
s
H
3
Nh,
S(CH2CH
2
hS. Bond length changes from Ru(III) to Ru(II) are predicted.
It is felt that in general the PKS model provides a simple and consistent
approach.
An experimental parameter which correlates well with the degree of
delocalization in the mixed-valence complex (A + ... A) is the compropor-
tionation constant for the reaction (34). The factors affecting Kcom have
(34)
been discussed in relation to several systems, some of them newly reported
(Table 1.2). For the complexes 2 Sutton and Taube(69) have considered
solvent interaction, stabilization of the mixed-valence state by resonance,
and destabilization of the Ru(II)-Ru(II) species owing to the fact that the
Ru(1I) ions are competing to delocalize 1r electrons on to the ligand 1r*
system. In a series of complexes with Kcom = 7-20 (Table 1.2) the solvent
effect is a major factor. Much stronger coupling is found with dicyanamide
ion as the bridging ligand, and participation of the Ru(III)-(radical ion)-
Ru(III) states is shown by the fact that with nonbridging, 1r-withdrawing
T
a
b
l
e

1
.
2
.

M
i
x
e
d
-
V
a
l
e
n
c
e

C
o
m
p
l
e
x
e
s

"
m
a
x
,

E
,

C
o
m
p
l
e
x
e
s

1
0
3
c
m
-
1

1
0
3

M
-
1

c
m
-
1

[
(
H
3
N
)
s
R
u
N
C
N
C
N
R
u
(
N
H
3
)
s
]
4
+

9
.
0
9

2
.
8
2

[
(
P
y
)
(
H
3
N
)
4
R
u
N
C
N
C
N
R
u
(
N
H
3
)
4
(
P
y
)
t
+

8
.
2
0

2
.
5
3

[
(
i
s
n
)
(
H
3
N
)
4
R
u
N
C
N
C
N
R
u
(
N
H
3
)
4
(
i
s
n
)
]
4
+

8
.
0
0

2
.
3
1

9
.
7
1

9
2
0

M
e

M
e

(
(
H
,
N
W
U
N
O
-
C
H
.
-
Q
N
R
U
(
N
H
,
)
,
]
'

1
1
.
2
4

1
6
5

[
(
H
3
N
h
R
U
N
Q
-
-
N

H

-
Q
N
R
U
(
N
H
3
)
6
]
S
+

1
0
.
8
7

1
0
.
1
0

[
(
H
3
N
h
R
U
N
Q
-
-
C
H
:
C
H
-
Q
R
U
(
N
H
3
)
s
l
S
+

1
0
.
4
2

7
6
0

R
e
f
.

3
4
0

6
9
a

1
5
5

6
9
a

7
5

6
9
a

2
0

6
9

9
.
8

6
9

2
6

6
9

1
4

6
9

'
-
0
<
:
>

'
-

;
:
:

"
"

;
:
:
,

;
:
:

;
:
:
"
.

"
"

<
:
>

.
.
.
.

;
:
:
;
.

[
(
H
3
N
)
S
R
U
N
Q
-
C
:
C
-
Q
N
R
U
(
N
H
3
)
5
]
5
+

1
0
.
8
7

6
4
0

[
(
H
3
N
)
S
R
U
O
C
H
2
0
N
R
U
(
N
H
3
)
S
]
5
+

1
2
.
3
5

3
0

[
(
p
h
e
n
h
R
u
O
(
C
2
H
4
O
)
n
R
u
(
p
h
e
n
h
]
5
+

8
.
8
1
e

[
(
N
H
3
)
4
R
u
L
R
u
(
N
H
3
)
4
]
3
+

d

6
.
6
2

4
3
0

[
(
N
H
3
)
4
R
u
L
R
u
(
b
p
y
h
]
3
+

d

1
0
.
4
1

2
5
0

[
(
b
y
p
h
R
u
L
R
u
(
b
p
y
h
]
3
+

d

[
(
p
h
e
n
h
C
I
R
u
(
p
y
z
)
R
u
C
l
(
p
h
e
n
h
]
3
+

e

7
.
6
0

6
5
0

[
o
-
C
6
H
4
(
C
H
2
S
h
F
e
(
I
I
I
)
(
S
h
F
e
(
I
I
)
(
S
C
H
2
h
C
6
H
4
-
o
]
3
-
g

g

0
.
1

M

H
C
I
,

2
S
C
.

b
n

=

S
.

o

S
o
l
i
d

s
t
a
t
e
,

K
B
r

p
e
l
l
e
t
.

d

L

=

2
,
S
-
p
y
r
a
z
i
n
e

d
i
c
a
r
b
o
x
y
l
a
t
e
.

D
a
t
a

r
e
p
o
r
t
e
d

a
l
s
o

f
o
r

s
u
b
s
t
i
t
u
t
e
"

p
h
e
n

d
e
r
i
v
a
t
i
v
e
s
.

f

C
H
3
C
N
;

l
l
G
o
o
m

=

2
.
3

k
c
a
l

m
o
l
-
I
.

u
v
-
v
i
s
i
b
l
e

s
p
e
c
t
r
a

r
e
p
o
r
t
e
d

b
u
t

I
T

b
a
n
d
s

n
o
t

a
s
s
i
g
n
e
d
.

1
3
.
8

6
.
7

1
b

1
.
2

x

1
0
5

4
.
9

x

1
0
1
3

1
.
1

X

1
0
3

f

2
.
6

X

1
0
5

6
9

6
9

7
1

1
1
4

1
1
4

1
1
4

1
1
5

7
4

0
\

'
"

I
:
l
.
.
.

,

;
:
s

'
"
'

'
"

g

3

>
<

'
"

"
-
.
.
.
.
.

'
C

20
1 General and Theoretical
ligands, the coupling is decreased(69a) (d. above, p. 7). For the complexes
3 [M = Cu(II), M' = Cu(I)] Gagne et al. have included a contribution from
3
magnetic stabilization of Cu(II)-Cu(II) by calculating the singlet-triplet
(70)
separatlon.
In a series of complexes of the type 4 the electronic coupling is
negligible (Kcorn - 1) but the IT band is observed and must correspond to
an essentially outer-sphere transfer process(71) (the linked-pair
mechanism).(72)
A remarkable series of polynuclear mixed-valence complexes is
exemplified by compound 5 (B = bipyridyl). Spectra and electrochemical
1. 7 Electron Transfer in the Solid State 21
data are reported, and Kearn for reactions such as [2,2 ... 2,2] +
[3, 3 ... 3, 3] 2[3, 2 ... 3, 2], where the numbers denote oxidation
states at the Ru centers. (73)
The compound 6(74) is a model of the Fe
2
S6 unit found in ferredoxin
proteins. (75) Electrochemical and homogeneous chemical redox reactions
establish the existence of the series Fe(III)Fe(III), Fe(III)Fe(II), and
Fe(II)Fe(II), and epr and Mossbauer spectra show the middle members to
be of the class II mixed-valence type.(74) As yet, however, the IT band has
not been detected.
The comproportionation constants referred to here may be compared
with values ranging from 8 x 10
4
to 1 X 10
9
for directly metal-metal-
bonded dimers, as obtained from electrochemical oxidation studies of, e.g.,
[
Cr
2(map )4]
1
+
/
2+, [
Re
2
CI
4(dppe h]01+/2+. (76)
1.7. Electron Transfer in the Solid State t
The conductivity of one-dimensional metal complexes has been
reviewed. (77) The influence of structure is emphasized, as are the interesting
structural changes which occur when the fractional oxidation state is varied.
Measurements of dielectric relaxation frequency have been used to obtain
ac and dc conductivities, the latter of which lead to the rate of hopping
("site-transfer") conductivity. In the double salt K
3
(Mn04)z, these data
give the rate of the outer-sphere(7S) electron transfer reaction (35). A
MnO:;- ... ... MnO:;- (35)
different technique for measuring the same physical process is time domain
reflectometry.(79) Applied to the mixed-valence solid EU
3
S4, it gives the
rate of Eu(III) + Eu(II) electron transfer in good agreement with previous
Mossbauer work.
The V(V)/(IV) exchange occurs in partially reduced polyvanadic acid
gels. These are class II mixed-valence species, and have been studied
by esr, optical spectroscopy, and electrical conductivity measurements(SO)
(Table 1.1).
t See also footnote. p. 16.
The mixed-valence ion [P
2
W IS vIVvi 0
62
]10- exhibits rapid intra-
molecular electron hopping as shown by esr line broadening. Moreover,
the esr spectra show partial delocalization of the electrons from V(IV) to
the neighboring V(V), so that the complex must be classed as a borderline
case between localized class II and delocalized class III. (81) A similar sugges-
tion has been made(82) for the complex [Fe30(00CCH3)6L3], (L =
H
2
0,py). Mossbauer line-broadening data indicate the Fe(III)/Fe(II) elec-
tron transfer process, with low activation energies. (83)
The infrared spectrum of Cs
4
[Sb(V)CI
6
][Sb(III)CI
6
] shows some
remarkably temperature-sensitive bands in the region 100-300 cm -1. They
are assigned(84) to vibrations of the Sb(III)CI
6
unit, and it is suggested that
this effect is due to the thermal electron transfer process Sb(IV) + Sb(III).
It should be noted, however, that this requires a "hopping" frequency of
the order of 10 12 s -1, whereas Atkinson and Day(I06) assigned a much lower
frequency, from conductivity studies. t
Using the resonance Raman effect, Hester and Nour(8S) have assigned
the Fe(II) ....... Co (III) intervalence transitions in the complexes
[(NC)sFe(II)CNCo(III)(CN)st- and [(NC)sFe(II)CNCo(III)(edta)]5-.
Detailed analysis of the CN stretching modes also confirms the ground
state valency assignments as shown. In the linear chain complexes
[Pt(LLh][Pt(LLhX
2
]X
4
(LL = diamine, X = Br (86) or I (87)) the Pt(II)-Pt-
Pt(IV) intervalence band is coupled to the symmetrical stretch, X-Pt-X of
the Pt(IV) units, as in other complexes of this type.
Electronic Raman spectroscopy has attracted increasing attention in
recent years,(88) and a theory of the resonance electronic Raman effect has
now been given.(89) Wong and Schatz have also discussed in detail the
electronic Raman effect as applied to mixed-valence systems(90) particularly
the Pt(IV)-Pt(II) linear chain compounds (following their previous study(91)
of the conventional resonance Raman spectra of these materials).
t The authors of Ref. 84 assumed their data to be in agreement with Atkinson and Day, but
they appear to have identified w, of equation 2, Ref. 106 as the hopping frequency, instead
of K.
Chapter 2
Redox Reactions between
Metal Complexes
2.1. Introduction
In this chapter, the electron transfer reactions between metal ion
complexes have been reviewed in a systematic fashion which emphasizes
the role of the reductant ion. It has been found convenient in the past to
condense rate data and these are found in Table 2.1. Major theoretical
advances have been made in this area over the period covered but these
have been dealt with in Chapter 1. Similarly, papers which report no new
rate data but theoretical treatment of existing data have not been included.
In some cases, papers capable of inclusion in more than one section have
been included where the balance of the chapter demands.
2.2. Titanium (III)
Reduction of [Ru(enhf+ by TiOH
2
+ is outer sphere(l) and the activa-
tion enthalpy for the reaction suggests a closer approach of the reactants
than might be expected. It is thought that the chelate ring directs the
reductant and enhances t2g/t2g overlap. Inner-sphere mechanisms are pro-
posed(2) for reduction of [Co(NH3)SX]2+ complexes by Ti
3
+ where X- is a
good bridging ligand such as F- or OH-. In these cases the rates are close
to the substitution-limited inner-sphere value. Salicylate, salH-, has proved
to be an effective bridge(3) in the electron transfer from Ti3+ to
23

T
a
b
l
e

2
.
1
.

R
a
t
e

C
o
n
s
t
a
n
t
s

a
n
d

T
h
e
r
m
o
d
y
n
a
m
i
c

P
a
r
a
m
e
t
e
r
s

f
o
r

R
e
a
c
t
i
o
n
s

b
e
t
w
e
e
n

M
e
t
a
l

I
o
n

C
o
m
p
l
e
x
e
s

a
t

2
5
C

/
L
,

k
,

i
l
H
t
,

i
l
S
t
,

R
e
a
c
t
i
o
n

M

M
-
1
8
-
1

k
c
a
l

m
o
l
-
I

c
a
l

K
-
1

m
o
l
-
I

R
e
f
.

T
i
t
a
n
i
u
m
(
I
I
I
l

[
R
u
(
e
n
h
f
+

+

T
i
O
H
2
+

0
.
1

k
/
[
H
+
]

5

(
8
-
l
l

1
3

-
1
6

1

[
C
o
(
N
H
3
l
s
B
r
]
2
+

+

T
i
O
H
2
+

1
.
0

0
.
1
8

2

[
C
o
(
N
H
3
l
s
F
f
+

+

T
e
+

1
.
0

1

x

1
0
3

2

c
i
s
-
[
C
o
(
e
n
)
z
(
H
2
0
l
O
H
f
+

+

T
i
3
+

1
.
0

5
0

2

t
r
a
n
s
-
[
C
o
(
e
n
h
(
H
2
0
l
O
H
]
2
+

+

T
i
3
+

1
.
0

2
0

2

c
i
s
-
[
C
o
(
e
n
h
(
H
2
0
l
O
H
]
2
+

+

T
i
O
H
2
+

1
.
0

3

X

1
0
3

2

t
r
a
n
s
-
[
C
o
(
e
n
h
(
H
2
0
l
O
H
]
2
+

+

T
i
O
H
2
+

1
.
0

4

X

1
0
3

2

[
R
u
(
N
H
3
l
s
s
a
I
H
]
2
+

+

T
i
3
+

1
.
0

6

X

1
0
2

3

[
R
u
(
N
H
3
l
s
N
C
s
f
+

+

[
T
i
(
H
E
D
T
A
l
l

2
.
0

2
.
8

x

1
0
4

5

[
R
u
(
N
H
3
l
s
N
C
s
f
+

+

T
i
3
+

2
.
0

8
4
0

8
.
5

1
2

5

[
C
o
(
N
H
3
l
4
C
2
0
4
t

+

T
i
3
+

1
.
0

0
.
0
4

6

[
C
o
(
N
H
3
l
4
C
2
0
4
t

+

[
T
i
(
C
2
0
4
W

1
.
0

1
0

6

[
C
o
(
N
H
3
l
4
C
2
0
4
t

+

[
T
i
(
C
2
0
4
h
r

1
.
0

4
0
0

6

V
a
n
a
d
i
u
m
(
I
I
l

t
r
a
n
s
-
[
R
u
(
e
n
h
C
h
t

+

V
2
+

0
.
5

1
.
2
1

x

1
0
3

8

t
r
a
n
s
-
[
R
u
(
e
n
h
B
r
C
l
f

+

V
2
+

0
.
5

2
.
2
5

x

1
0
3

8

t
r
a
n
s
-
[
R
u
(
e
n
h
C
I
B
r
t

+

V
2
+

0
.
5

2
.
2
5

x

1
0
3

8

t
r
a
n
s
-
[
R
u
(
e
n
h
B
r
2
t

+

V
2
+

0
.
5

3
.
0
7

x

1
0
3

8

t
r
a
n
s
-
[
R
u
(
e
n
h
I
2
t

+

V
2
+

0
.
5

1
.
2
7

x

1
0
4

8

t
r
a
n
s
-
[
R
u
(
2
,
3
,
2

-
t
e
t
l
C
l
2
t

+

V
2
+

0
.
5

2
.
0
3

x

1
0
3

8

t
r
a
n
s
-
[
R
u
(
[
1
4
]
-
a
n
e
N
4
l
C
h
f

+

V
2
+

0
.
5

3
.
6
8

x

1
0
3

8

t
r
a
n
s
-
[
R
u
(
[
1
5
]
a
n
e
N
4
l
C
h
t

+

V
2
+

0
.
5

3
.
5
6

x

1
0
3

8

t
r
a
n
s
-
[
R
u
(
M
e
6
[
1
6
]
a
n
e
N
4
l
C
I
2
t

+

V
2
+

0
.
5

7
.
7
8

x

1
0
3

8

r
a
c
-
[
R
u
(
M
e
6
[
1
4
]
a
n
e
N
4
l
C
h
t

+

V
2
+

0
.
5

7
.
6
9

x

1
0
3

8

[
C
o
(
N
H
3
l
s
0
2
C
C
H
2
0
2
C
C
s
H
4
N
H
]
3
+

+

V
2
+

1
.
0

1
.
1
8

1
0
0

[
C
o
(
N
H
3
l
s
0
2
C
(
C
H
2
h
0
2
C
C
s
H
4
N
H
]
3
+

+

V
2
+

1
.
0

1
.
7
3

1
0
0

[
C
o
(
N
H
3
)
s
0
2
C
H
(
C
H
3
)
0
2
C
C
s
H
4
N
H
]
3
+

+

y
2
+

1
.
0

1
.
6
5

1
0
0

[
C
o
(
N
H
3
)
s
0
2
C
-
O
-
C
6
H
4
C
H
2
N
C
s
H
4
C
O
N
H
2
f
+

+

V
2
+

1
.
0

0
.
8
7

1
0
0

[
C
o
(
N
H
3
)
S
0
2
C
C
H
2
0
2
C
-
m
-
C
s
H
4
N
H
]
3
+

+

y
2
+

1
.
0

0
.
7
4

1
0
0

[
C
o
(
N
H
3
)
s
0
2
C
C
H
3
f
+

+

V
2
+

1
.
0

1
.
1
5

1
0
1

[
C
o
(
N
H
3
)
s
0
2
C
C
H
2
C
H
3
]
2
+

+

y
2
+

1
.
0

1
.
0
9

1
0
1

[
C
o
(
N
H
3
)
s
C
H
2
C
(
C
H
3
b
f
+

+

V
2
+

1
.
0

0
.
3
6

1
0
1

[
C
o
(
N
H
3
)
s
0
2
C
(
C
H
3
b
]
2
+

+

V
2
+

1
.
0

0
.
2
2

1
0
1

[
C
o
(
N
H
3
)
s
0
2
C
H
2
C
6
H
s
f
+

+

V
2
+

1
.
0

0
.
9
2

1
0
1

[
C
o
(
N
H
3
)
S
0
2
C
6
H
4
-
0
-
C
H
3
f
+

+

V
2
+

1
.
0

0
.
6
2

1
0
1

[
C
o
(
N
H
3
)
s
0
2
C
H
2
N
H
(
O
)
C
C
H
3
]
2
+

+

V
2
+

1
.
0

1
.
4
5

1
0
1

[
C
o
(
N
H
3
)
S
0
2
C
C
H
2
N
H
3
f
+

+

V
2
+

1
.
0

0
.
8
5

1
0
1

[
C
o
(
N
H
3
)
s
0
2
C
C
H
2
N
(
C
H
3
h
f
+

+

V
2
+

1
.
0

0
.
2
4

1
0
1

[
C
o
(
N
H
3
)
s
0
2
C
C
(
N
H
3
)
(
C
H
3
h
f
+

+

V
2
+

1
.
0

0
.
1
4

1
0
1

[
C
o
(
N
H
3
)
s
0
2
C
C
H
(
N
H
3
)
C
H
3
]
3
+

+

V
2
+

1
.
0

0
.
3
8

1
0
1

[
C
o
(
N
H
3
)
s
0
2
C
(
C
H
2
h
N
H
3
f
+

+

V
2
+

1
.
0

0
.
9
9

1
0
1

[
C
o
(
N
H
3
)
s
0
2
C
(
C
H
2
b
N
H
3
]
3
+

+

V
2
+

1
.
0

0
.
5
5

1
0
1

[
C
o
(
N
H
3
)
s
0
2
C
C
H
2
P
y
]
3
+

+

V
2
+

1
.
0

1
.
1
4

1
0
1

[
C
o
(
N
H
3
)
S
0
2
C
C
6
H
4
-
0
-
N
H
3
f
+

+

V
2
+

1
.
0

0
.
3
8

1
0
1

C
h
r
o
m
i
u
m
(
I
I
)

t
r
a
n
s
-
[
R
u
(
e
n
h
C
I
2
]
+

+

C
r
2
+

0
.
5

3
0
.
2

5

-
3
6

7

t
r
a
n
s
-
[
R
u
(
2
,

3
,

2
t
e
t
)
C
l
2
t

+

C
r
2
+

0
.
5

4
7
.
3

6
.
5

-
3
0

7

t
r
a
n
s
-
[
R
u
(
[
1
4
]
a
n
e
N
4
)
C
h
t

+

C
r
2
+

0
.
5

6
4
.
4

6
.
5

-
2
9

7

t
r
a
n
s
-
[
R
u
(
e
n
h
B
r
C
l
t

+

C
r
2
+

0
.
5

3
7
.
0

8

t
r
a
n
s
-
[
R
u
(
e
n
h
C
I
B
r
t

+

C
r
2
+

0
.
5

3
7
.
0

8

t
r
a
n
s
-
[
R
u
(
e
n
}
z
B
r
2
t

+

C
r
2
+

0
.
5

7
6
.
3

8

t
r
a
n
s
-
[
R
u
(
e
n
}
z
I
2
]
+

+

C
r
2
+

0
.
5

2
9
5

8

t
r
a
n
s
-
[
R
u
(
[
1
5
]
a
n
e
N
4
)
C
I
2
t

+

C
r
2
+

0
.
5

1
1
6

8

m
e
s
o
-
[
R
u
(
M
e
6
[
1
4
]
a
n
e
N
4
)
C
h
t

+

C
r
2
+

0
.
5

4
.
9
5

x

1
0
3

8

r
a
c
-
[
R
u
(
M
e
6
[
1
4
]
a
n
e
N
4
)
C
I
2
t

+

C
r
2
+

0
.
5

3
.
7
5

x

1
0
3

8

[
C
o
(
N
H
3
)
s
N
C
C
H
2
C
0
2
H
]
3
+

+

C
r
2
+

0
.
5

2
.
3
4

x

1
0
-
2

1
7
.
5

-
1
5
.
2

9

[
C
o
(
N
H
3
)
s
N
C
C
H
2
C
o
2
f
+

+

C
r
2
+

0
.
5

2
.
1
1

9

t
-
.
.
)

[
C
o
(
N
H
3
)
s
N
C
C
H
3
f
+

+

C
r
2
+

0
.
5

9
.
4

x

1
0
-
3

1
0
.
3

-
3
3
.
1

9

V
.

I
\
J

T
a
b
l
e

2
.
1
.

(
c
o
n
t
i
n
u
e
d
)

0
-
I
L
,

k
,

!
!
H
t
,

t
l
s
t
,

R
e
a
c
t
i
o
n

M

M
-
1

S
-
1

k
c
a
l
m
o
l
-
1

c
a
l

K
-
1

m
o
l
-
1

R
e
f
.

C
h
r
o
m
i
u
m
(
I
I
)
-
c
o
n
t
d
.

[
C
o
(
N
H
3
)
s
N
C
(
C
H
2
h
C
N
]

+

C
r
2
+

0
.
5

2
.
5
4

x

1
0
-
2

9
.
5

-
3
4
.
1

9

[
C
o
(
N
H
3
l
s
N
C
C
H
2
C
O
N
H
2
]

+

C
r
2
+

0
.
5

2
.
6
1

x

1
0
-
2

9
.
0

-
3
5
.
6

9

[
C
o
(
N
H
3
)
s
N
C
C
H
2
C
0
2
C
H
3
]

+

C
r
2
+

0
.
5

2
.
3
4

x

1
0
-
2

9
.
5

-
3
4
.
2

9

[
C
o
(
N
H
3
l
s
N
C
C
H
2
C
0
2
r

+

C
r
2
+

0
.
5

2
.
1
1

1
2
.
5

-
1
5
.
2

9

[
C
r
(
N
H
3
l
s
(
o
-
A
B
H
)
]
3
+

+

C
r
2
+

1
.
0

6
.
2

x

1
0
-
4

1
1

2
9

1
0

[
C
r
(
N
H
3
l
s
(
o
-
A
B
)
]
2
+

+

C
r
2
+

1
.
0

1
.
1
5

x

1
0
-
1

1
0

[
C
r
(
N
H
3
l
s
(
o
-
A
B
b
e
n
z
a
l
d
e
h
y
d
e
)
f
+

+

C
r
2
+

1
.
0

4
.
0
0

x

1
0
-
2

1
1

2
8

1
0

[
C
r
(
N
H
3
)
s
(
o
-
A
B
s
a
l
i
c
y
l
a
l
d
e
h
y
d
e
)
f
+

1
.
0

3
.
6
1

1
2

2
6

1
0

[
C
r
(
N
H
3
)
s
(
o
-
A
B
v
a
n
i
l
l
i
n
)
]
2
+

1
.
0

3
.
5
5

1
2

2
6

1
0

[
C
r
(
N
H
3
)
s
(
m
-
A
B
H
)
]
3
+

1
.
0

3
.
8
5

1
0

3
1

1
0

[
C
r
(
N
H
3
)
s
(
m
-
A
B
b
e
n
z
l
d
e
h
y
d
e
)
]
2
+

1
.
0

3
.
8
0

1
0

3
3

1
0

[
C
r
(
N
H
3
)
s
(
m
-
A
B
s
a
l
i
c
y
l
a
l
d
e
h
y
d
e
)
f
+

1
.
0

3
.
7
6

9

3
5

1
0

[
C
r
(
N
H
3
)
s
(
m
-
A
B
v
a
n
i
l
l
i
n
)
]
2
+

1
.
0

3
.
6
2

9
1

3
5

1
0

[
C
r
(
N
H
3
l
s
(
p
-
A
B
H
)
]
3
+

1
.
0

4
.
6
5

9

3
5

1
0

[
C
r
(
N
H
3
l
s
(
p
-
A
B
b
e
n
z
a
l
d
e
h
y
d
e
)
]
2
+

1
.
0

4
.
4
7

9

3
5

1
0

[
C
r
(
N
H
3
l
s
(
p
-
A
B
s
a
l
i
c
y
l
a
l
d
e
h
y
d
e
)
f
+

1
.
0

4
.
1
0

1
0

3
5

1
0

[
C
r
(
N
H
3
)
s
(
p
-
A
B
v
a
n
i
l
l
i
n
)
]
2
+

1
.
0

3
.
8
0

1
0

3
2

1
0

[
C
o
(
N
H
3
)
4
(
g
l
y
c
i
n
e
)
]
2
+

+

C
r
2
+

1
.
0

6
.
4

7
.
1

-
3
1

1
1

[
C
o
(
N
H
3
)
4
(
D
,
L
-
a
l
a
n
i
n
e
)
f
+

+

C
r
2
+

1
.
0

1
.
7

9
.
2

-
2
7

1
1

[
C
o
(
N
H
3
)
4
(
D
,
L
-
p
h
e
n
y
l
a
l
a
n
i
n
e
)
f
+

+

C
r
2
+

1
.
0

2
.
3

1
0
.
1

-
2
3

1
1

[
C
o
(
E
D
T
A
)
r

+

C
r
2
+

1
.
0

6
.
6

x

1
0
3

1
3

[
C
o
(
H
E
D
T
A
)
(
O
H
2
)
]

+

C
r
2
+

1
.
0

7
.
6

x

1
0
3

1
3

[
C
o
(
H
E
D
T
A
)
C
I
r

+

C
r
2
+

1
.
0

>
2
.
6

x

1
0
6

1
3

[
C
o
(
N
H
3
)
S
0
2
C
C
H
2
N
C
s
H
4
C
O
N
H
2
]
3
+

+

C
r
2
+

1
.
0

6
.
6

x

1
0
2

1
0
0

+

C
r
2
+

1
.
0

4
.
2

1
0
0

[
C
o
(
N
H
3
l
s
0
2
(
C
H
2
h
0
2
C
C
s
H
4
N
H
]
3
+

+

C
r
2
+

1
.
0

1
.
8
9

1
0
0

[
C
o
(
N
H
3
)
S
0
2
C
H
(
C
H
3
)
0
2
C
C
s
H
4
N
H
]
3
+

+

C
r
2
+

1
.
0

3
.
0

1
0
0

[
C
o
(
N
H
3
)
S
0
2
C
-
O
-
C
6
H
4
C
H
2
N
C
s
H
4
C
O
N
H
2
f
+

+

C
r
2
+

1
.
0

2
.
2

1
0
0

[
C
o
(
N
H
3
l
s
0
2
C
C
H
2
0
2
C
-
m
-
C
s
H
4
N
H
]
3
+

+

C
r
2
+

1
.
0

0
.
1
2
6

1
0
0

[
C
o
(
N
H
3
)
s
0
2
C
C
H
3
f
+

+

C
r
2
+

1
.
0

0
.
3
5

1
0
1

[
C
o
(
N
H
3
l
s
0
2
C
C
H
2
C
H
3
f
+

+

C
r
2
+

1
.
0

0
.
1
7
3

1
0
1

[
C
o
(
N
H
3
l
s
0
2
C
H
2
C
(
C
H
3
h
]
2
+

+

C
r
2
+

1
.
0

5
.
5

x

1
0
-
2

1
0
1

[
C
o
(
N
H
3
)
s
0
2
C
C
(
C
H
3
h
f
+

+

C
r
2
+

1
.
0

7
.
0

X

1
0
-
3

1
0
1

[
C
o
(
N
H
3
)
S
0
2
C
C
H
2
C
6
H
s
f
+

+

C
r
2
+

1
.
0

0
.
1
6

1
0
1

[
C
o
(
N
H
3
)
S
0
2
C
C
6
H
4
-
0
-
C
H
3
f
+

+

C
r
2
+

1
.
0

8
.
7

x

1
0
-
2

1
0
1

[
C
o
(
N
H
3
)
s
0
2
C
C
H
2
N
H
(
O
)
C
C
H
3
]

+

C
r
2
+

1
.
0

0
.
2
6

1
0
1

[
C
o
(
N
H
3
)
S
0
2
C
H
2
N
H
3
]
3
+

+

C
r
2
+

1
.
0

6
.
4

x

1
0
-
2

1
0
1

[
C
o
(
N
H
3
)
S
0
2
C
C
H
2
N
H
2
C
H
3
]
3
+

+

C
r
2
+

1
.
0

4
.
4

x

1
0
-
2

1
0
1

[
C
o
(
N
H
3
)
S
0
2
C
C
H
2
N
H
(
C
H
3
h
f
+

+

C
r
2
+

1
.
0

3
.
8

x

1
0
-
2

1
0
1

[
C
o
(
N
H
3
)
S
0
2
C
C
H
2
N
(
C
H
3
h
f
+

+

C
r
2
+

1
.
0

1
.
6
X
1
0
-
2

1
0
1

[
C
o
(
N
H
3
)
s
0
2
C
C
(
N
H
3
h
]
3
+

+

C
r
2
+

1
.
0

3
.
3

x

1
0
-
3

1
0
1

[
C
o
(
N
H
3
)
S
0
2
C
H
(
N
H
3
)
C
H
3
]
3
+

+

C
r
2
+

1
.
0

2
.
6

x

1
0
-
2

1
0
1

[
C
o
(
N
H
3
l
s
0
2
C
(
C
H
2
h
N
H
3
]
3
+

+

C
r
2
+

1
.
0

9
.
8

x

1
0
-
2

1
0
1

[
C
o
(
N
H
3
)
s
0
2
C
(
C
H
2
h
N
H
3
]
3
+

+

C
r
2
+

1
.
0

0
.
1
3
6

1
0
1

[
C
o
(
N
H
3
)
s
0
2
C
C
H
2
P
y
]
3
+

+

C
r
2
+

1
.
0

3
.
9

x

1
0
-
2

1
0
1

[
C
o
(
N
H
3
)
S
0
2
C
C
6
H
4
-
0
-
N
H
3
]
3
+

+

C
r
2
+

1
.
0

8
.
6

x

1
0
-
3

1
0
1

F
e
3
+

+

[
C
r
(
b
i
p
y
h
]
2
+

1
.
4
4

x

1
0
9

1
5

F
e
3
+

+

[
C
r
(
4
,
4
'
-
P
h
2
b
i
p
y
h
]
2
+

1
.
6

x

1
0
9

1
5

F
e
3
+

+

[
C
r
(
4
,
4
'
-
M
e
2
b
i
p
y
h
f
+

1
.
0
6

x

l
O
t
o

1
5

F
e
3
+

+

[
C
r
(
5
-
C
l
p
h
e
n
h
f
+

7
.
0

x

1
0
8

1
5

F
e
3
+

+

[
C
r
(
5
-
B
r
p
h
e
n
h
f
+

6
.
1

x

1
0
8

1
5

F
e
3
+

+

[
C
r
(
5
-
P
h
p
h
e
n
h
f
+

1
.
4

x

1
0
9

1
5

F
e
3
+

+

[
C
r
(
5
-
M
e
p
h
e
n
h
]
2
+

1
.
9

x

1
0
9

1
5

F
e
3
+

+

[
C
r
(
p
h
e
n
h
f
+

2
.
0

x

1
0
9

1
5

F
e
3
+

+

[
C
r
(
5
,

6
-
M
e
2
p
h
e
n
h
]
2
+

1
.
3

x

1
0
9

1
5

F
e
3
+

+

[
C
r
(
4
,
7
-
P
h
2
p
h
e
n
b
f
+

2
.
7

x

1
0
9

1
5

F
e
3
+

+

[
C
r
(
4
,
7
-
M
e
2
p
h
e
n
h
]
2
+

1
.
6

x

1
0
9

1
5

t
-
.
:
.

F
e
3
+

+

[
C
r
(
3
.
4
,
7
,
8
-
M
e
4
p
h
e
n
h
]
2
+

7
.
1

x

1
0
8

1
5

'
I

I
\
.
)

T
a
b
l
e

2
.
1
.

(
c
o
n
t
i
n
u
e
d
)

0
0

,
.
"
,

k
,

1
!
J
l
*
,

f
l
.
S
t
,

R
e
a
c
t
i
o
n

M

M
-
1

S
-
1

k
c
a
l
m
o
l
-
1

c
a
l

K
-
1

m
o
l
-
1

R
e
f
.

C
h
r
o
m
i
u
m
(
I
I
)
-
c
o
n
t
d
.

C
u
2
+

+

[
C
r
(
C
H
2
O
H
)
]
2
+

1
.
0

0
.
0
3
6

1
8
.
2

-
6

1
7

k
/
[
H
+
]

0
.
2
5

(
s

-
1
)

2
1

8

1
7

C
u
2
+

+

[
C
r
(
C
H
(
C
H
3
)
O
H
)
]
2
+

1
.
0

0
.
6
8

1
7

k
/
[
H
+
]

1
.
4
6

(
S
-
I
)

C
u
2
+

+

[
C
r
(
C
(
C
H
3
h
O
H
)
f
+

1
.
0

0
.
7
7

1
7

C
u
2
+

+

[
C
r
(
C
H
C
F
3
O
H
)
]
2
+

k
/
[
H
+
]

0
.
5
7
4

(
s
-
1
)

1
.
0

k
/
[
H
+
]

2

x

1
0
-
4

(
S
-
I
)

1
7

F
e
3
+

+

[
C
r
(
C
H
2
O
H
)
]
2
+

1
.
0

0
.
2
2

1
2

-
2
2

1
7

k
/
[
H
+
]

0
.
4
9
6

(
S
-
I
)

2
3

1
5

1
7

F
e
3
+

+

[
C
r
C
H
(
C
H
3
)
O
H
]
2
+

1
.
0

0
.
7
1

1
7

k
/
[
H
+
]

0
.
4
8
1

(
s
-
1
)

1
7

F
e
3
+

+

[
C
r
C
(
C
H
3
h
O
H
]
2
+

1
.
0

3
.
7
9

1
7

k
/
[
H
+
]

1
.
9
0

(
S
-
I
)

1
7

F
e
3
+

+

[
C
r
(
C
H
(
C
F
3
)
O
H
)
]
2
+

1
.
0

k
/
[
H
+
]

0
.
1
2
7

(
S
-
I
)

1
7

F
e
3
+

+

[
C
r
(
C
H
(
C
H
3
)
O
E
t
)
]
2
+

1
.
0

0
.
0
8
2

1
7

k
/
[
H
+
]

0
.
0
4

(
S
-
1
)

1
7

F
e
3
+

+

[
C
r
(
C
H
2
O
M
e
)
f
+

1
.
0

0
.
0
0
6
2

1
7

k
/
[
H
+
]

0
.
0
1
2
7

(
S
-
1
)

1
7

H
g
2
+

+

[
C
r
(
C
(
C
H
3
h
O
H
)
]
2
+

1
.
0

1
6
6

1
9

k
/
[
H
+
]

4
6
7

(
S
-
I
)

1
9

H
g
2
+

+

[
C
r
(
C
H
(
C
H
3
)
O
E
t
)
]
2
+

1
.
0

k
/
[
H
+
]

0
.
5
3
5

(
S
-
I
)

1
9

H
g
2
+

+

[
C
r
(
C
H
(
C
H
3
)
O
H
)
f
+

1
.
0

k
/
[
H
+
]

4
.
1
1

(
S
-
I
)

1
9

I
r
o
n
(
I
I
)

t
r
a
n
s
-
[
C
o
(
D
H
h
p
y
C
I
]

+

F
e
2
+

(
3
0
C
)

1
.
0

0
.
0
5
1

2
1

t
r
a
n
s
-
[
C
o
(
D
H
)
(
D
H
2
)
p
y
C
I
t

+

F
e
2
+

(
3
0
C
)

1
.
0

0
.
7
6

2
1

t
r
a
n
s
-
[
C
o
(
D
H
h
p
y
B
r
]

+

F
e
2
+

(
3
0
C
)

1
.
0

0
.
0
7
1

2
1

t
r
a
n
s
-
[
C
o
(
D
H
)
(
D
H
2
)
p
y
B
r
t

+

F
e
2
+

(
3
0
C
)

1
.
0

1
.
2
1

2
1

t
r
a
n
s
-
[
C
o
(
D
H
h
p
y
I
]

+

F
e
2
+

(
3
0
C
)

1
.
0

0
.
0
7
8

2
1

t
r
a
n
s
-
[
C
o
(
D
H
)
(
D
H
2
)
p
y
l
t

+

F
e
2
+

(
3
0
C
)

1
.
0

1
.
9
1

2
1

t
r
a
n
s
-
[
C
o
(
D
H
h
(
N
3
h
r

+

F
e
2
+

(
3
0
C
)

1
.
0

0
.
0
9
8

2
1

4
.
5

2
2

t
r
a
n
s
-
[
C
o
(
D
H
h
(
C
N
S
h
r

+

F
e
2
+

(
3
0
C
)

1
.
0

0
.
0
2
3

2
1

1
.
3

2
2

[
C
o
(
p
h
e
n
h
]
3
+

+

f
e
r
r
o
c
e
n
e

5
0
%

M
e
O
H

3
.
1

x

1
0
4

1
1
.
0

-
1

3
6

[
C
o
(
d
m
g
h
(
B
F
h
t

+

f
e
r
r
o
c
e
n
e

C
H
3
C
N

1
.
6

x

1
0
4

8
.
4

-
1
1

3
7

F
e
r
r
i
c
i
n
i
u
m
+

+

h
o
r
s
e

h
e
a
r
t

c
y
t

c
(
I
1
)

0
.
5
0

6
.
2

x

1
0
6

3
8

[
C
u
(
4
,
7
-
(
P
h
S
0
3
l
z
-
2
,
9
-
M
e
2
p
h
e
n
l
z
f
+

+

[
F
e
(
C
N
)
6
t
-
0
.
1

2
.
7

x

1
0
5

6
1

[
C
u
(
4
,
7
-
(
P
h
S
0
3
h
-
2
,
9
-
M
e
2
p
h
e
n
h
f
+

+

[
F
e
(
e
d
t
a
)
]
2
-
0
.
1

4
.
2

x

1
0
5

6
1

C
u
2
+

+

c
y
t

c
(
I
1
)

0
.
1

1
.
7

x

1
0
4

6
3

[
C
u
(
E
t
S
(
C
H
2
h
h
N
H
C
H
2
-
o
-
p
y
]
2
+

+

c
y
t

c
(
I
I
)

0
.
1

1
.
7

x

1
0
3

6
3

[
C
u
(
0
2
C
O
H
2
S
C
H
2
C
0
2
)
]

+

c
y
t

c
(
I
I
)

0
.
1

1
.
7

x

1
0
2

6
3

[
C
u
(
0
2
C
C
H
2
S
(
C
H
2
h
S
C
H
2
C
0
2
)
]

+

c
y
t

c
(
I
1
)

0
.
1

5
.
1

x

1
0
3

6
3

[
C
u
(
0
2
C
C
H
2
S
(
C
H
2
h
S
C
H
2
C
0
2
)
]

+

c
y
t

c
(
I
1
)

0
.
1

3
6

6
3

[
C
u
(
1
4
a
n
e
S
4
)
]

+

c
y
t

c
(
I
I
)

0
.
1

2
.
4

x

1
0
6

6
3

C
u
2
+

+

c
y
t

c
(
I
I
)

0
.
1

5
.
7

6
4

C
u
C
I
+

+

c
y
t

c
(
I
1
)

0
.
1

2
.
3

x

1
0
2

6
4

C
u
C
I
2

+

c
y
t

c
(
I
1
)

0
.
1

5
.
6

x

1
0
3

6
4

C
o
b
a
l
t
(
I
1
)

C
o
3
+

+

[
C
o
(
M
e
2
[
1
4
]
4
,
7
-
d
i
e
n
e
N
4
-
6
-
o
n
e
)
(
H
2
O
h
f
+

3
.
0

3
.
g

x

1
0
2

4
0

C
o
3
+

+

[
C
o
(
M
e
2
P
y
o
[
1
4
]
t
r
i
e
n
e
N
4
)
(
H
2
O
h
f
+

3
.
0

4
.
8

x

1
0
2

4
0

C
o
3
+

+

[
C
o
(
M
e
4
[
1
4
]
t
e
t
r
a
e
n
e
N
4
)
(
H
2
O
h
f
+

3
.
0

3
.
3
7

x

1
0
2

1
2

-
6

4
0

C
o
3
+

+

[
C
o
(
M
e
6
[
1
4
]
4
,
1
l
-
d
i
e
n
e
N
4
)
(
H
2
O
h
f
+

3
.
0

6
6

4
0

C
o
3
+

+

[
C
o
(
[
1
4
]
a
n
e
N
4
)
(
H
2
O
h
]
2
+

3
.
0

7
.
0

x

1
0
2

4
0

C
o
3
+

+

[
C
o
(
[
1
5
]
a
n
e
N
4
)
(
H
2
O
h
]
2
+

3
.
0

2
.
5
7

x

1
0
2

4
0

C
o
H

+

[
C
o
(
s
e
p
)
]
2
+

3
.
0

7
.
0

x

1
0
2

4
0

[
F
e
(
C
N
)
6
]
3
-
+

[
C
o
(
E
D
T
A
)
O
H
]
3
-
0
.
2
6

6
.
8
4

4
1

[
F
e
(
C
N
)
6
]
3
-
+

[
C
o
(
E
D
T
A
)
f
-
0
.
2
6

2
.
6
1

4
1

[
C
o
(
M
e
4
[
1
6
]
t
e
h
r
a
e
n
e
N
4
)
C
I
2
t

+

[
C
o
(
[
1
4
]
a
n
e
N
4
)
(
H
2
O
h
f
+

0
.
5

2
.
0

x

1
0
4

4
2

[
F
e
(
b
i
p
y
h
]
3
+

+

[
C
o
(
[
1
4
]
a
n
e
N
4
)
(
H
2
O
h
]
2
+

0
.
1

1
.
6

x

1
0
5

4
2

I
'
-
l

[
F
e
(
p
h
e
n
h
]
H

+

[
C
o
(
[
1
4
]
a
n
e
N
4
)
(
H
2
O
h
f
+

0
.
2

1
.
6

x

1
0
5

4
2

'
C

T
a
b
l
e

2
.
1
.

(
c
o
n
t
i
n
u
e
d
)

/
L
,

k
,

!
!
H
t
,

/
:
:
;
.
S
*
,

R
e
a
c
t
i
o
n

M

M
-
1

S
-
I

k
c
a
l
m
o
l
-
I

c
a
l

K
-
1

m
o
l
-
I

R
e
f
.

C
o
b
a
l
t
(
I
I
)
-
c
o
n
t
d
.

[
C
o
(
M
e
2
P
y
o
[
1
4
]
t
r
i
e
n
e
N
4
)
(
H
2
0
h
]
3
+

+

[
C
o
(
s
e
p
)
]
2
+

0
.
1

5
.
4

x

1
0
4

4
3

[
C
o
(
M
e
4
[
1
4
]
t
e
t
r
a
e
n
e
N
4
)
(
H
2
0
}
z
]
3
+

+

[
C
o
(
s
e
p
)
f
+

0
.
1

6
.
8

x

1
0
4

4
3

[
C
o
(
M
e
2
[
1
4
]
1
,
1
1
-
d
i
e
n
e
N
4
-
1
3
-
o
n
e
)
(
H
2
0
h
f
+

+

[
C
o
(
s
e
p
)
]
2
+

0
.
1

3
.
0

x

1
0
4

4
3

[
C
o
(
M
e
6
[
1
4
]
4
,
1
1
-
d
i
e
n
e
N
4
-
o
n
e
)
(
H
2
0
h
]
3
+

+

[
C
o
(
s
e
p
)
f
+

0
.
1

7
.
9

x

1
0
2

4
3

[
C
o
(
[
1
4
]
a
n
e
N
4
)
(
H
2
0
h
]
3
+

+

[
C
o
(
s
e
p
)
f
+

0
.
1

6
.
5

x

1
0

4
3

[
C
o
(
M
e
2
P
y
o
[
1
4
]
t
r
i
e
n
e
N
4
)
(
H
2
0

h
]
3
+

+

[
C
O
(
M
e
4
[

1
4
]
t
e
t
r
a
e
n
e
N
)
(
H
2
0

h
f
+

1
.
0

7
.
0

X

1
0
-
2

4
3

[
C
O
(
M
e
2
P
Y
O
[

1
4
]
t
r
i
e
n
e
N
4
)
(
H
2
0

h
]
3
+
[
C
o
(
[
1
4
]
a
n
e
N
4
)
(
H
2
0

h
f
+

1
.
0

8
.
5

X

1
0
-
2

4
3

[
C
o
(
M
e
4
[
1
4
]
t
e
t
r
a
e
n
e
N
4
(
H
2
0
h
f
+

+

[
C
o
(
[
1
4
]
a
n
e
N
4
)
(
H
2
O
h
f
+

1
.
0

0
.
1
3

4
3

[
C
o
(
M
e
2
[
1
4
]
1
,

1
1
-
d
i
e
n
e
N
4
-
1
3
-
o
n
e
)
(
H
2
0
h
]
3
+

+

[
C
o
(
M
e
2
P
y
o
[
1
4
]
t
r
i
e
n
e
N
4
)
(
H
2
O
h
]
2
+

1
.
0

4
.
6

x

1
0
-
2

4
3

[
C
o
(
M
e
2
[
1
4
]
1
,
1
1
-
d
i
e
n
e
N
4
-
1
3
-
o
n
3
)
(
H
2
0
h
]
3
+

+

[
C
o
(
M
e
4
[
1
4
]
t
e
t
r
a
e
n
e
4
)
(
H
2
0
h
f
+

1
.
0

2
.
5

x

1
0
-
2

4
3

[
C
o
(
M
e
2
[
1
4
]
1
,
1
1
-
d
i
e
n
e
N
4
-
1
3
-
o
n
e
)
(
H
2
0
h
f
+

+

[
C
o
(
[
1
4
]
a
n
e
N
4
)
(
H
2
O
h
f
+

1
.
0

0
.
1
8

4
3

[
C
o
(
M
e
6
[
1
4
]
4
,
1
1
-
d
i
e
n
e
N
4
)
(
H
2
0

h
f
+

+

[
C
O
(
M
e
2
P
Y
O
[

1
4
]
t
r
i
e
n
e
N
4
)
(
H
2
0

h
]
2
+

1
.
0

2
.
0

X

1
0
-
3

4
3

[
C
O
(
M
e
6
[

1
4
]
4
,
1
1
-
d
i
e
n
e
N
4
)
(
H
2
0

h
]
3
+

+

[
C
O
(
M
e
4
[

1
4
]
t
e
t
r
a
e
n
e
N
4
)
(
H
2
0

h
]
2
+

1
.
0

1
.
3

X

1
0
-
3

4
3

[
C
o
(
T
P
P
)
(
p
y
h
t

+

[
C
o
(
T
P
P
)
]

C
D
C
h

1
.
9
1

x

1
0
-
2

4
5

[
C
o
(
T
P
P
)
(
p
y
h
t

+

[
C
o
(
T
P
P
)
p
y
]

C
D
C
I
3

1
.
2
9

x

1
0
-
1

8
.
3

-
2
3

4
5

[
C
o
(
T
P
P
)
(
p
y
h
t

+

[
C
o
(
T
P
P
)
(
p
y
h
]

C
D
C
h

9
.
6
9

4
5

[
C
o
(
T
P
P
)
C
I
]

+

[
C
o
(
T
P
P
)
]

C
D
C
I
3

2
.
7

x

1
0
4

1
0
.
3

-
3
.
6

4
6

[
C
o
(
T
P
P
)
I
]

+

[
C
o
(
T
P
P
)
]

C
D
C
h

8
.
1
7

x

1
0
6

4
.
9

-
1
0
.
5

4
6

[
C
o
(
T
P
P
)
B
r
]

+

[
C
o
(
T
P
P
)
]

C
D
C
I
3

3
.
7
3

X

1
0
5

6
.
2

-
1
2
.
1

4
6

[
C
o
(
T
P
P
)
S
C
N
]

+

[
C
o
(
T
P
P
)
]

C
D
C
I
3

6
.
4
9

X

1
0
5

5
.
9

-
1
2
.
2

4
6

[
C
o
(
T
P
P
)
N
3
]

+

[
C
o
(
T
P
P
)
]

C
D
C
I
3

2
.
1
3
x
1
0
6

5
.
8

-
1
0
.
1

4
6

[
I
r
C
I
6
]
2
-
+

[
C
o
(
D
p
n
H
)
M
e
2
]

(
C
H
3
C
N
,
0
.
1
)

4
.
0

x

1
0
2

4
7

[
I
r
C
I
6
f
-
+

[
C
o
(
T
I
M
)
M
e
2
t

(
C
H
3
C
N
,
0
.
1
)

2
.
8

x

1
0
3

4
7

[
F
e
(
b
i
p
y
h
]
3
+

+

[
C
o
(
D
p
n
H
)
M
e
2
]

(
C
H
3
C
N
,
0
.
1
)

1
0
6

4
7

[
F
e
(
5
-
N
0
2
p
h
e
n
h
]
3
+

+

[
C
o
(
D
p
n
H
)
M
e
t

(
C
H
3
C
N
,
0
.
1
)

2
.
9

4
7

[
F
e
(
p
h
e
n
h
]
3
+

+

[
C
o
(
D
p
n
H
)
M
e
t

(
C
H
3
C
N
,
0
.
1
)

1
.
6

x

1
0
-
2

4
7

[
F
e
(
b
i
p
y
h
]
3
+

+

[
C
o
(
D
p
n
H
)
E
t
t

(
C
H
3
C
N
,
0
.
1
)

3
.
0

x

1
0
-
1

4
7

[
F
e
(
5
-
N
0
2
p
h
e
n
h
]
3
+

+

[
C
o
(
D
p
n
H
)
E
t
t

(
C
H
3
C
N
,
0
.
1
)

5
.
4

x

1
0
2

4
7

[
I
r
C
I
6
f
-
+

[
C
o
(
D
p
n
H
)
E
t
]
+

(
C
H
3
C
N
,
0
.
1
)

1
0
-
6

4
7

N
i
c
k
e
l
(
I
I
)

[
C
o
O
H
2
+

+

[
N
i
(
[
1
4
]
a
n
e
N
4
)
]
2
+

3
.
0

4
.
7

x

1
0
5

6
.
5

-
1
0

5
0

C
o
3
+

+

[
N
i
(
M
e
6
[
1
4
]
-
4
,
1
l
-
d
i
e
n
e
N
4
)
]
2
+

1
.
5

2
.
8
0

x

1
0
2

4
0

[
C
u
(
H
_
2
A
i
b
3
)
]

+

[
C
u
(
H
_
2
A
i
b
3
)
r

0
.
1

5
.
5

x

1
0
4

7
.
0

-
1
3

6
7

[
C
u
(
H
_
2
(
H
_
2
G
2
f
3
A
)
)
]

+

[
I
r
C
I
6
P
-
0
.
1

5
.
0

x

1
0
7

6
8

[
I
r
C
I
6
f
-
+

[
C
U
(
H
-
2
A
3
l
r

0
.
1

3
.
7

x

1
0
7

6
8

[
I
r
C
I
6
]
2
-
+

[
C
u
(
H
-
2
L
3
)
r

0
.
1

6
.
9

x

1
0
7

6
8

[
I
r
C
I
6
f
-
+

[
C
U
(
H
-
2
G
3
A
O
C
H
3
l
r

0
.
1

1
.
2

x

1
0
8

6
8

[
I
r
C
I
6
f
-
+

[
C
U
(
H
-
3
G
4
a
)
r

0
.
1

1
.
1

x

1
0
9

6
8

[
I
r
C
I
6
f
-
+

[
C
U
(
H
-
3
G
3
a
)
r

0
.
1

7
.
6

x

1
0
8

6
8

[
I
r
C
I
6
f
-
+

[
C
u
(
H
_
3
P
G
2
a
)
r

0
.
1

8
.
7

x

1
0
8

6
8

[
I
r
C
I
6
f
-
+

[
C
U
(
H
_
3
G
4
)
]
2
-
0
.
1

1
.
5

x

1
0
8

6
8

[
I
r
C
I
6
f
-
+

[
C
u
(
H
_
3
A
3
)
]
2
-
0
.
1

1
.
4

x

1
0
8

6
8

[
I
r
C
I
6
f
-
+

[
C
u
(
H
_
3
A
4
)
]
2
-
0
.
1

4
.
6

x

1
0
7

6
8

[
I
r
C
I
6
f
-
+

[
C
U
(
H
_
3

V
4
)
]
2
-
0
.
1

2
.
9

x

1
0
7

6
8

[
I
r
C
I
6
]
2
-
+

[
C
u
(
H
-
4
C
)
f
-
0
.
1

4
.
0

x

1
0
8

6
9

[
C
u
(
H
_
2
A
i
b
3
)
]

+

[
C
u
(
H
_
4
C
)
]
2
-
0
.
1

1
.
5
5

x

1
0
6

6
9

M
o
l
y
b
d
e
n
u
m

[
I
r
C
I
6
]
2
-
+

M
o
3
O
!
+

2
.
0

k
/
[
H
+
]

1
.
3
6

(
S
-
I
)

1
4
.
1

-
9
.
6

7
0

[
F
e
(
p
h
e
n
h
]
3
+

+

M
o
3
O
!
+

2
.
0

k
/
[
H
+
]

0
.
5
3

(
s

-
I
)

7
0

[
M
O
O
(
S
2
C
S
C
H
(
C
H
3
h
h
]

+

[
M
o
O
(
S
2
C
S
C
H
(
C
H
3
h
l
z
]

C
2
H
4
C
I
z

3
.
2

x

1
0
4

6
.
2

-
2
0

7
2

.
.
.
.
.
.

T
a
b
l
e

2
.
1
.

(
c
o
n
t
i
n
u
e
d
)

/
L
,

k
,

t
:
.
H
*
,

A
S
"
,

R
e
a
c
t
i
o
n

M

M
-
1

S
-
l

k
c
a
l

m
o
l
-
1

c
a
l

K
-
1

m
o
l
-
1

R
e
f
.

R
u
t
h
e
n
i
u
m
(
I
I
)

[
R
u
(
b
i
p
y
h
p
y
O
H
2
]
2
+

+

[
R
u
(
b
i
p
y
h
p
y
O
]
2
+

0
.
1

2
.
1
0

x

l
O
s

2
.
2
3

-
2
9
.
5

7
4

[
R
u
(
b
i
p
y
h
p
y
O
H
f
+

+

[
R
u
(
b
i
p
y
h
p
y
O
H
f
+

0
.
1

2
.
9

x

1
0
3

7
4

[
C
o
(
N
H
3
)
4
o
X
t

+

[
R
u
(
N
H
3
)
6
f
+

2
.
0

7
.
8

1
4
.
8

-
6

7
5

[
C
o
(
N
H
3
)
s
o
x
H
f
+

+

[
R
u
(
N
H
3
)
6
]
2
+

2
.
0

1
1
8
.
1

7
5

k
/
[
H
+
]

0
.
5

(
S
-
l
)

[
C
o
(
N
H
3
)
4
o
X
t

+

[
R
u
(
N
H
3
l
s
H
2
0
f
+

2
.
0

3
.
7

1
6
.
2

-
3

7
5

[
C
o
(
N
H
3
l
s
o
x
H
f
+

+

[
R
u
(
N
H
3
)
s
H
2
0
f
+

2
.
0

7
.
1
8

7
5

k
/
[
H
+
]

0
.
1
0

(
S
-
l
)

[
R
u
(
N
H
3
)
4
o
X
t

+

[
R
u
(
N
H
3
)
6
]
2
+

0
.
1
0

3
.
6

7
6

[
R
u
(
N
H
3
)
4
o
x
H
f
+

+

[
R
u
(
N
H
3
)
6
f
+

0
.
1
0

2
6
.
4

7
6

[
R
u
(
N
H
3
l
s
o
x
H
f
+

+

[
R
u
(
N
H
3
)
6
f
+

0
.
1
0

1
.
3

7
6

[
R
u
(
N
H
3
l
s
o
x
H
2
]
3
+

+

[
R
u
(
N
H
3
)
6
]
2
+

0
.
1
0

1
3
.
6

7
6

[
R
u
(
N
H
3
l
s
O
A
c
]
2
+

+

[
R
u
(
N
H
3
l
6
f
+

0
.
1
0

4
.
8

7
6

[
R
u
(
N
H
3
)
s
O
A
c
H
]
3
+

+

[
R
u
(
N
H
3
l
6
f
+

0
.
1
0

8
2
.
5

7
6

[
R
u
(
N
H
3
l
4
o
x
t

+

[
R
u
(
N
H
3
l
s
O
H
2
f
+

0
.
1
0

0
.
8

7
6

[
R
u
(
N
H
3
)
4
o
x
H
f
+

+

[
R
u
(
N
H
3
l
s
O
H
2
]
2
+

0
.
1
0

1
2
.
8

7
6

[
R
u
(
N
H
3
l
s
o
x
H
]
2
+

+

[
R
u
(
N
H
3
)
s
O
H
2
f
+

0
.
1
0

0
.
5

7
6

[
R
u
(
N
H
3
)
s
o
x
H
2
f
+

+

[
R
u
(
N
H
3
)
s
O
H
2
]
2
+

0
.
1
0

7
.
5

7
6

[
R
u
(
N
H
3
l
s
O
A
c
f
+

+

[
R
u
(
N
H
3
l
s
O
H
2
]
2
+

0
.
1
0

2
.
6

7
6

[
R
u
(
N
H
3
l
s
O
A
c
H
]
3
+

+

[
R
u
(
N
H
3
l
s
O
H
2
]
2
+

0
.
1
0

4
2
.
8

7
6

[
R
u
(
4
,
4
'
-
M
e
2
b
i
p
y
)
(
h
f
a
c
h
t

+

[
R
u
(
4
,
4
'
-
M
e
2
b
i
p
y
)
(
h
f
a
c
h
]

C
H
3
C
N

4
.
5

x

1
0
6

7
7

[
R
u
(
4
,
4
'
-
M
e
2
b
i
p
y
)
(
a
c
a
c
h
t

+

[
R
u
(
4
,
4
'
-
M
e
2
b
i
p
y
)
(
a
c
a
c
h
]

C
H
3
C
N

1
.
4

x

1
0
8

3
.
3

7
7

[
R
u
(
h
f
a
c
h
]

+

[
R
u
(
h
f
a
c
h
r

C
H
3
C
N

5

x

1
0
6

7
.
0

7
7

[
C
u
(
4
,
7
-
(
P
h
S
0
3
h
-
2
,
9
-
M
e
2
p
h
e
n
h
f
-
+

[
R
u
(
N
H
3
)
s
p
y
]
2
+

0
.
1

1
.
5

x

1
0
7

6
1

[
C
o
(
M
e
2
P
y
o
[
1
4
]
t
r
i
e
n
e
N
4
)
(
H
2
0
h
]
3
+

+

[
R
u
(
N
H
3
)
6
f
+

0
.
1

4
.
7
5

x

1
0
4

4
3

[
C
o
(
M
e
2
[
1
4
]
-
1
,
1
1
-
d
i
e
n
e
N
4
-
1
3
-
o
n
e
)
(
H
2
0
h
]
3
+

+

[
R
u
(
N
H
3
)
6
]
2
+

0
.
1

1
.
2
0

x

l
O
S

4
3

C
o
3
+

+

[
R
u
(
N
H
3
)
4
(
p
h
e
n
)
]
2
+

3
.
0

4
.
0

X

1
0
4

4
0

[
C
o
(
N
H
3
)
s
0
2
C
C
H
3
f
+

+

[
R
u
(
N
H
3
)
6
]
2
+

O
.
S
O

2
.
2

X

1
0
-
2

1
0
1

[
C
o
(
N
H
3
)
S
0
2
C
C
H
2
C
(
C
H
3
h
f
+

+

[
R
u
(
N
H
3
)
6
]
2
+

O
.
S

6
.
9

X

1
0
-
2

1
0
1

[
C
o
(
N
H
3
l
s
0
2
C
C
(
C
H
3
h
f
+

+

[
R
u
(
N
H
3
)
6
]
2
+

O
.
S

8
.
7

X

1
0
-
3

1
0
1

[
C
o
(
N
H
3
l
s
0
2
C
C
H
2
C
6
H
s
]
2
+

+

[
R
u
(
N
H
3
)
6
f
+

O
.
S

S
.
6

X

1
0
-
2

1
0
1

[
C
o
(
N
H
3
l
s
0
2
C
C
H
2
N
H
C
(
0
)
C
H
3
f
+

+

[
R
u
(
N
H
3
)
6
]
2
+

O
.
S

4
.
8

X

1
0
-
2

1
0
1

[
C
o
(
N
H
3
l
s
0
2
C
C
H
2
N
H
3
f
+

+

[
R
u
(
N
H
3
)
6
]
2
+

O
.
S

8
.
2

X

1
0
-
2

1
0
1

[
C
o
(
N
H
3
)
S
0
2
C
C
H
2
N
(
C
H
3
h
]
3
+

+

[
R
u
(
N
H
3
)
6
f
+

O
.
S

0
.
2
7

1
0
1

[
C
o
(
N
H
3
l
s
0
2
C
C
H
2
P
y
]
3
+

+

[
R
u
(
N
H
3
)
6
]
2
+

O
.
S

0
.
2
9

1
0
1

[
(
N
H
3
)
s
C
o
(
I
L
-
0
2
)
C
o
(
N
H
3
)
s
t
+

+

[
*
R
u
(
b
i
p
y
h
f
+

1
.
0

1
.
3
4

X

1
0
7

8
2

[
(
N
H
3
)
4
C
O
(
1
L
0
2
I
L
N
H
2
)
C
o
(
N
H
3
)
S
+

+

[
*
R
u
(
b
i
p
y
h
]
2
+

1
.
0

3
.
4

X

l
O
S

8
2

[
(
e
n
)
z
C
o
{
l
0
2
,

I
L
N
H
2
)
C
o
(
e
n
)
z
]
3
+

+

[
*
R
u
(
b
i
p
y
h
]
2
+

1
.
0

2
.
4
S

X

1
0
6

8
1

[
(
b
i
p
y
)
z
C
o
(
1
L

O
2
,

I
'

N
H
2
)
C
o
(
b
i
p
y
)
z
]
3
+

+

[
*
R
u
(
b
i
p
y
h
]
2
+

1
.
0

3
.
0
3

X

1
0
8

8
1

[
(
p
h
e
n
h
C
o
(
1
L

0
2
1
'

N
H
2
)
C
o
(
p
h
e
n
)
z
]
3
+

+

[
*
R
u
(
b
i
p
y
h
]
2
+

1
.
0

3
.
6
4

X

1
0
8

8
1

[
C
o
(
p
h
e
n
h
]
3
+

+

[
*
R
u
(
b
i
p
y
h
]
2
+

1
.
0

1
.
2
4

X

1
0
9

8
3

[
R
h
(
b
i
p
y
h
]
3
+

+

[
*
R
u
(
S
-
C
l
p
h
e
n
h
f
+

O
.
S

4
.
1

x

1
0
8

8
7

[
R
h
(
b
i
p
y
h
]
3
+

+

[
*
R
u
(
b
i
p
y
h
f
+

O
.
S

6
.
2

X

1
0
8

8
7

[
R
h
(
b
i
p
y
h
]
3
+

+

[
*
R
u
(
p
h
e
n
h
]
2
+

O
.
S

9
.
9

x

1
0
8

8
7

[
R
h
(
b
i
p
y
h
]
3
+

+

[
*
R
u
(
4
,
4
'
-
M
e
2
b
i
p
y
h
f
+

O
.
S

1
.
1
4

x

1
0
9

8
7

[
R
h
(
b
i
p
y
h
]
3
+

+

[
*
R
u
(
4
,
7
-
M
e
2
p
h
e
n
h
f
+

O
.
S

1
.
2
S

x

1
0
9

8
7

[
R
h
(
p
h
e
n
h
]
3
+

+

[
*
R
u
(
S
-
C
l
p
h
e
n
h
f
+

O
.
S

S
.
7

x

1
0
8

8
7

[
R
h
(
p
h
e
n
h
]
3
+

+

[
*
R
u
(
b
i
p
y
h
f
+

O
.
S

6
.
8

X

1
0
8

8
7

[
R
h
(
p
h
e
n
h
f
+

+

[
*
R
u
(
p
h
e
n
h
]
2
+

O
.
S

1
.
1
6

x

1
0
9

8
7

[
R
h
(
p
h
e
n
h
f
+

+

[
*
R
u
(
4
,
4
'
-
M
e
2
p
h
e
n
h
f
+

O
.
S

1
.
3
7

x

1
0
9

8
7

[
R
h
(
p
h
e
n
h
f
+

+

[
*
R
u
(
4
,
7
-
M
e
2
p
h
e
n
h
f
+

O
.
S

1
.
4
7

x

1
0
9

8
7

[
R
h
(
b
i
p
y
h
f
+

+

[
*
R
u
(
S
-
C
l
p
h
e
n
h
]
2
+

O
.
S

2
.
(
x

1
0
8

9
0

[
R
h
(
S
-
M
e
p
h
e
n
h
]
3
+

+

[
*
R
u
(
S
-
C
l
p
h
e
n
h
f
+

O
.
S

1
.
6

x

1
0
8

9
0

[
R
h
(
4
,
4
'
-
M
e
2
b
i
p
y
h
]
3
+

+

[
*
R
u
(
S
-
C
l
p
h
e
n
h
]
2
+

O
.
S

1
.
0

X

1
0
6

9
0

[
R
h
(
S
-
B
r
p
h
e
n
h
]
3
+

+

[
*
R
u
(
b
i
p
y
h
f
+

O
.
S

l
o
S

X

1
0
9

9
0

[
R
h
(
S
-
C
l
p
h
e
n
h
]
3
+

+

[
*
R
u
(
b
i
p
y
h
]
2
+

O
.
S

l
o
S

X

1
0
9

9
0

[
R
h
(
S
-
p
h
p
h
e
n
h
f
+

+

[
*
R
u
(
b
i
p
y
h
]
2
+

O
.
S

1
.
6

X

1
0
9

9
0

[
R
h
(
p
h
e
n
h
]
3
+

+

[
*
R
u
(
b
i
p
y
h
]
2
+

O
.
S

4
.
0

X

1
0
8

9
0

[
R
h
(
b
i
p
y
h
]
3
+

+

[
*
R
u
(
b
i
p
y
h
f
+

O
.
S

6
.
0

X

1
0
8

9
0

\
.
.
;
,

T
a
b
l
e

2
.
1
.

(
c
o
n
t
i
n
u
e
d
)

"
"
"

1
1
-
,

k
,

l
!
J
{
*
,

t
:
.
S
*
,

R
e
a
c
t
i
o
n

M

M
-
1
8
-
1

k
c
a
l

m
o
l
-
1

c
a
l

K
-
1

m
o
l
-
1

R
e
f
.

R
u
t
h
e
n
i
u
m
(
I
I
)
-
c
o
n
t
d
.

[
R
h
(
4
,
7
-
M
e
2
p
h
e
n
h
f
+

+

[
*
R
u
(
b
i
p
y
h
]
2
+

O
.
S

1
.
7
3

x

1
0
9

9
0

[
R
h
(
S
,
6
-
M
e
2
p
h
e
n
h
]
3
+

+

[
*
R
u
(
b
i
p
y
h
]
2
+

O
.
S

3
.
0

X

1
0
8

9
0

[
R
h
(
S
-
M
e
p
h
e
n
h
]
3
+

+

[
*
R
u
(
b
i
p
y
h
]
2
+

O
.
S

4
.
0

X

1
0
8

9
0

[
R
h
(
4
,
4
'
-
M
e
2
b
i
p
y
h
f
+

+

[
*
R
u
(
b
i
p
y
h
]
2
+

O
.
S

3
.
0

X

1
0
7

9
0

[
R
h
(
b
i
p
y
h
]
3
+

+

[
*
R
u
(
S
-
M
e
p
h
e
n
h
f
+

O
.
S

7
.
0

x

1
0
8

9
0

[
R
h
(
S
,
6
-
M
e
2
p
h
e
n
h
f
+

+

[
*
R
u
(
S
-
M
e
p
h
e
n
h
]
2
+

O
.
S

1
.
3

x

1
0
9

9
0

[
R
h
(
S
-
M
e
p
h
e
n
h
]
3
+

+

[
*
R
u
(
S
-
M
e
p
h
e
n
h
]
2
+

O
.
S

1
.
0

x

1
0
9

9
0

[
R
h
(
4
,
4
'
-
M
e
2
b
i
p
y
h
]
3
+

+

[
*
R
u
(
S
-
M
e
p
h
e
n
h
f
+

O
.
S

4
.
9

x

1
0
8

9
0

[
R
h
(
b
i
p
y
h
]
3
+

+

[
*
R
u
(
p
h
e
n
h
f
+

O
.
S

6
.
0

x

1
0
8

9
0

[
R
h
(
S
,
6
-
M
e
2
p
h
e
n
h
]
3
+

+

[
*
R
u
(
p
h
e
n
h
]
2
+

O
.
S

9
.
5

x

1
0
8

9
0

[
R
h
(
S
-
M
e
p
h
e
n
h
]
3
+

+

[
*
R
u
(
p
h
e
n
h
f
+

O
.
S

9
.
8

x

1
0
8

9
0

[
R
h
(
4
,
4
'
-
M
e
2
b
i
p
y
h
]
3
+

+

[
*
R
u
(
p
h
e
n
h
]
2
+

O
.
S

2
.
0

x

1
0
8

9
0

[
R
h
(
b
i
p
y
h
]
3
+

+

[
*
R
u
(
4
,
7
-
M
e
2
p
h
e
n
h
f
+

O
.
S

9
.
0

x

1
0
8

9
0

[
R
h
(
S
,
6
-
M
e
2
p
h
e
n
h
]
3
+

+

[
*
R
u
(
4
,
7
-
M
e
2
p
h
e
n
h
f
+

O
.
S

1
.
6

x

1
0
9

9
0

[
R
h
(
S
-
M
e
p
h
e
n
h
f
+

+

[
*
R
u
(
4
,
7
-
M
e
2
p
h
e
n
h
f
+

O
.
S

1
.
3

x

1
0
9

9
0

[
R
h
(
4
,
4
'
-
M
e
2
b
i
p
y
h
]
3
+

+

[
*
R
u
(
4
,
7
-
M
e
2
p
h
e
n
h
]
2
+

O
.
S

1
.
2

x

1
0
9

9
0

E
u
r
o
p
i
u
m
(
I
I
)

[
C
o
(
N
H
3
)
s
N
3
f
+

+

E
u
2
+

1
.
0

3
.
S

X

1
0
2

9
9

[
C
o
(
N
H
3
)
s
N
0
3
f
+

+

E
u
2
+

1
.
0

1
.
2

X

1
0
2

9
9

[
C
o
(
N
H
3
)
s
N
C
s
f
+

+

E
u
2
+

1
.
0

3
0

9
9

[
C
o
(
N
H
3
)
s
P
0
4
r

+

E
u
2
+

1
.
0

2
9

9
9

[
C
o
(
N
H
3
)
s
N
0
2
f
+

+

E
u
2
+

1
.
0

4
3

9
9

[
C
o
(
N
H
3
)
s
O
N
O
f
+

+

E
u
2
+

1
.
0

S
8

9
9

[
C
o
(
N
H
3
)
S
0
2
C
C
H
2
N
C
s
H
4
C
O
N
H
2
]
3
+

+

E
u
2
+

1
.
0

1
.
6

X

1
0
2

1
0
0

[
C
o
(
N
H
3
)
s
0
2
C
C
H
2
0
2
C
C
s
H
4
N
H
f
+

+

E
u
2
+

1
.
0

6
2

1
0
0

+

E
u
2
+

1
.
0

2
2

1
0
0

[
C
o
(
N
H
3
h
0
2
C
H
(
C
H
3
)
0
2
C
C
s
H
4
N
H
]
3
+

+

E
u
2
+

[
C
o
(
N
H
3
)
S
0
2
C
-
O
-
C
6
H
4
C
H
2
N
C
s
H
4
C
O
N
H
2
]
3
+

+

E
u
2
+

[
C
o
(
N
H
3
h
0
2
C
C
H
2
0
2
C
-
m
-
C
s
H
4
N
H
]
3
+

+

E
u
2
+

[
C
o
(
N
H
3
)
s
0
2
C
C
H
3
]
2
+

+

E
u
2
+

[
C
o
(
N
H
3
h
0
2
C
C
H
2
C
(
C
H
3
h
f
+

+

E
u
2
+

[
C
o
(
N
H
3
)
s
0
2
C
C
(
C
H
3
h
]
2
+

+

E
u
2
+

[
C
o
(
N
H
3
h
0
2
C
C
H
2
C
6
H
s
f
+

+

E
u
2
+

[
C
o
(
N
H
3
)
S
0
2
C
C
6
H
4
-
0
-
C
H
3
f
+

+

E
u
2
+

[
C
o
(
N
H
3
h
0
2
C
C
H
2
N
H
C
(
O
)
C
H
3
f
+

+

E
u
2
+

[
C
o
(
N
H
3
h
0
2
C
C
H
2
N
H
3
]
3
+

+

E
u
2
+

[
C
o
(
N
H
3
h
0
2
C
C
H
2
N
(
C
H
3
h
]
3
+

+

E
u
2
+

[
C
o
(
N
H
3
h
0
2
C
C
(
N
H
3
)
(
C
H
3
)
z
]
3
+

+

E
u
2
+

[
C
o
(
N
H
3
h
0
2
C
C
H
(
N
H
3
)
C
H
3
]
3
+

+

E
u
2
+

[
C
o
(
N
H
3
)
s
0
2
C
(
C
H
2
)
z
N
H
3
]
3
+

+

E
u
2
+

[
C
o
(
N
H
3
)
s
0
2
C
(
C
H
2
h
N
H
3
]
3
+

+

E
u
2
+

[
C
o
(
N
H
3
h
0
2
C
C
H
2
P
y
]
3
+

+

E
u
2
+

[
C
o
(
N
H
3
)
S
0
2
C
C
6
H
4
-
0
-
N
H
3
f
+

+

E
u
2
+

1
.
0

1
.
0

1
.
0

1
.
0

1
.
0

1
.
0

1
.
0

1
.
0

1
.
0

1
.
0

1
.
0

1
.
0

1
.
0

1
.
0

1
.
0

1
.
0

1
.
0

3
2

1
1

1
.
1
7

2
.
4
3

0
.
4
5

0
.
1
8

1
.
1
0

0
.
7
0

2
.
0

1
.
8
3

0
.
7
4

0
.
1
9

0
.
6
8

1
.
2
8

1
.
0

0
.
8
2

0
.
4
1

1
0
0

1
0
0

1
0
0

1
0
1

1
0
1

1
0
1

1
0
1

1
0
1

1
0
1

1
0
1

1
0
1

1
0
1

1
0
1

1
0
1

1
0
1

1
0
1

1
0
1

36
2 Reactions between Metal Complexes
[Ru(NH
3
hSaIH]2+. An inner-sphere complex is formed with a second-order
rate constant of 6.3 x 10
2
M-
1
S -1 and the electron transfer rate is in excess
of 10
5
s-t, much greater than the calculated outer-sphere rate of 60 S-1
due to the favorable t2g/t2g overlap.
Reduction(4) of [VO(HEDTA)r by [Ti(HEDTA)H
2
0] is independent
of [VO(HEDTA)-] and involves acid chelate ring rupture in the reductant
with a rate of 73.6 s -1 at 25.2C, pH 5.0 and 0.5 M ionic strength. The
reaction is complicated by formation of binuclear species including a Ti(III)-
O-V(IV) complex which is in the wrong configuration for electron transfer.
Thiocyanate can bridge(5) between [Ru(NH
3
hNCS]2+ and
[Ti(HEDTA)H
2
0] or Ti3+. Protonation of [Ru(NH
3
hNCS]2+ inhibits the
reaction by destroying the lead-in group.
A brief report of the reduction of [Co(NH
3
)4C
2
0
4
t by Te+,
[Ti(C
2
0
4
)t, and [Ti(C
2
0
4
hr has appeared(6) in an effort to establish the
role of bridging oxalate. The reactions are inner sphere and have rates in
the order 0.04M-
1
s-t, 10M-
1
s-
1
and 400M-
1
s-t, respectively, in
0.15 M [H+] at 1.0 M ionic strength. It is thought that protonation of the
oxalate-bridged intermediate competes with electron transfer in contrast
to the corresponding reduction of ruthenium(III) where cross-bridge elec-
tron transfer is much more favorable.
2.3. Chromium(II) and (III)
The chromium (II) reductions of a number of trans-dihalide
ruthenium(III) complexes(7.S) are inner sphere in nature with halide bridging
groups. Reaction rates are sensitive to steric effects, whereas the corre-
sponding reductions by vanadium(II) show little steric variation, exceed
the V
2
+ ligand substitution rate, and must be considered outer sphere.
Outer-sphere Cr
2
+ reductions of nitrite-bonded pentaamine cobalt(I1I)
complexes are reported. (9) In contrast to other species examined, the
cyanoacetate complex shows acid dependence behavior consistent with
formation of a bridged intermediate (1) in which outer-sphere electron
[(NH
3
)sCo(III)N=CCH
2
C0
2
Cr(II)(H
2
0)st+
1
transfer leads to the [(H
2
0hCr02CCH
2
CN]2+ product. A similar acid
dependence has been noted(1O) in the reduction of the o-aminobenzoate
complex where an inner-sphere bridged electron transfer has been sug-
gested. Detection(ll) of O-bonded chromium(III) amino acid products in
the Cr
2
+ reduction of N,O-chelated amino acid complexes of cobalt(III)
2.4 [ron(Il) 37
suggests that an inner-sphere mechanism is operating in contrast to an
earlier report.(12) The rates are faster than those of [(NH
3
)sCo(O-
aminoacidH)]3+ complexes due to greater accessibility of the carboxylate
group on chelation and lowering of the charge.
Reduction of [Co(EDTA)r by Cr
2
+ shows(13) a reactivity pattern
corresponding to other inner-sphere reactions of this oxidant and its deriva-
tivesY4) The product is a carboxylate-bound EDTA complex of
chromium(III).
Photoreduction of chromium(III) polypyridyl complexes by Fe
2
+ allows
examination of the thermal reverse reaction.(15) For a series of complexes,
reactions with Fe3+ show very similar rate constants reflecting internal
activation free energies which do not differ markedly.
Permanganate oxidation(16) of the chromium(III) complexes
[H2Cr2(tartrateh(bipyh] and [HCr2(tartratehbipyr results in formation
of the bis-oxalato complexes. No monotartrate bridged complex is detected
which may imply that both diols are cleaved simultaneously or that the
monobridged complex is more reactive. The chromium(III) products of
oxidation of the bis(d-tartrate) and bis(meso-tartrate) complexes,
[Cr(OX)zbipyr, have opposite signs at 513 nm in their CD spectra and
racemize with half-lives of 48 and 46 min, respectively.
The chromium(III) a-hydroxyalkyl complexes(17) of the type
[(H
2
0)sCrCH
2
0H]2+ can be oxidized by Fe3+ or Cu
2
+ to give initially Fe
2
+
or Cu+, Cr
2
+, and the corresponding aldehyde. The dominant pathway in
the rate law is inhibited by [H+] and a mechanism involving complexation
with subsequent rate-determining electron transfer is proposed. Using the
methoxy compound [(H20)sCrCH
2
0CH
3
]2+ severely retards the reaction
suggesting binding to the oxidant through the a-hydroxy group. Some
confirmatory evidence for this presented(18) by way of the acidity depen-
dence in the reaction with V0
2
+. With Hg2+, electron transfer occurs with
a number of hydroxyalkyls but with the -CH
2
0H and -CH
2
0CH
3
derivatives, an electrophilic substitution resulting in the organomercurial
is noted. (19)
2.4. Iron (II)
The reagent TI(S04)z is the main oxidant in the reaction with iron (II)
in the presence of sulfate ions.(20) Iron(III) inhibits the reaction suggesting
participation by TI(II). An inner-sphere halide bridged mechanism is pro-
posed(21) for the Fe2+ reduction of trans-[Co(DH)zpyX] where DH- is
dimethylglyoximate anion and X is the halogen ion. Rate constants for both
uncatalyzed and base-catalyzed pathways show an increase in the order
38
Cl- < Br - < r. A similar mechanism is proposed(22) for the trans-azido
and trans-thiocyanato complexes.
The effects of SDS micelles on the rate of outer-sphere oxidation
of Fe2+ by [IrCI
6
]2- and [Os(bipyh]3+ have been investigated.(23) An
electrostatic model is used to calculate the localized concentrations of
positive ions with the negatively charged micelles and allows separation
of non electrostatic effects.
In a reexamination(24) of the volume of activation, !:J.. V*, of the inner-
sphere reduction of [Co(enhChr by Fe
2
+ in DMSO, conditions have been
extended to allow separation of the complexation, K, and electron transfer,
keh steps as in equation (1). These have reaction and activation volumes,
[ ) ]
+ 2+ K [ + 2+] k
et
d (1)
Co(en 2Ch + Fe Co(enhCI
2
, Fe pro ucts
respectively, of + 15.6 cm
3
mol-
1
and -13.6 cm
3
mol-
1
but the data do not
provide enough information to ascertain if there are two bridging chlorine
atoms.(25) Similar studies have been carried out on reduction of
[Co(NH
3
)sN
3
f+ in DMSO(26) and comparisons drawn with activation para-
meters in aqueous media. The differences can be ascribed to changes in
solvation of the ions and the resulting changes in steric crowding.
An electrochemical method(27) in which one of the reagents is trapped
in a polyelectrolyte film on the electrode surface has been used to determine
self-exchange rates for [IrCI
6
f-
/3
- and [Fe(CN)6]3-
/
4- of around
10
6
M-
1
S-1 and 10
7
M-
1
s-1, respectively. The latter value is higher than
comparable homogeneous rates but is consistent with the reduction of
electrostatic repulsion by the polyelectrolyte. Similar techniques have also
been used to measure rates of thermodynamically unfavorable reaction. (28)
Ion pairs are formed(29) in [Fe(CN)6]4- reduction of [Co(NH
3
)sL]3+
complexes where L is a substituted pyridine ligand. The magnitudes of the
association constants, Table 2.2, are consistent with approaches of
[Fe(CN)6]4- to the coordinated-ammonia side of the oxidant. The electron
transfer rates are relatively insensitive to structure once thermodynamic
forces have been accounted for and are similar to corresponding rates for
bridged electron transfer.
In an attempt(30) to examine the chemical mechanism where electron
transfer between two complexes takes place with a ligand radical intermedi-
ate, reactions of [Co(NH
3
)6]3+ with a series of pyridine-carboxylate radicals
are compared with internal electron transfers in [Co(NH
3
)sL']2+ species
where L is same pyridine-carboxylate ligand, this time coordinated directly
to the cobalt(III) center. Although other factors are important, the reduc-
tion potential of the ligand-ligand radical is a major factor in determining
the rate of internal electron transfer. Electron transfer solely through a
carboxylate linkage is generally an intramolecular outer-sphere process.
2.4 [ron(ll)
39
Good relationships are found(31) between thermodynamic data and
optical charge transfer transitions in a series of ion pairs of [Ru(NH
3
hL]3+
where L is a pyridine derivative, with [Fe(CN)6t-, [Ru(CN)6t-, and
[OS(CN)6]4-. The transitions are substantially independent of the reducing
metal ion and calculations suggest that these ion pairs also involve contact
on the amine side of the ruthenium complex.
With [Co(NH3)simidazole]3+ reaction(32) with [Fe(CNhOH
2
]3-, ion
pair formation with a stability constant of 670 M-
1
precedes inner-sphere
complexation to give [(NH
3
)sCo(imid)Fe(CNh] with a rate constant of
4.9 s -1 at 25C and 0.1 M ionic strength. Internal electron transfer with a
rate of 0.165 s -1 is faster than for corresponding pyrazine and 4,4' -bipy
bridged complexes and there is an apparent inverse relationship with
distance. This effect is ascribed to solvent polarization.
A similar study(33) is reported for reduction of [Co(NH
3
)sL]3+ com-
plexes where L is 3- or 4-cyanopyridine. Linkage isomers with cobalt
binding through the pyridine or cyano nitrogen are considered and outer-
sphere association prior to formation of a bridge with [Fe(CN)s(H
2
0)]3-
is detected in all cases. However, for cyanide-bound ions, this complex is
a "dead end" and electron transfer takes place through the outer-sphere
complex with rates 0.71 and 0.46 S-1 for 3- and 4-cyano derivatives,
respectively, while pyridine-bound nitrogen complexes undergo internal
electron transfer with rate constants of 3.0 x 10-
3
and 0.16s-
1
for 3- and
4-cyano derivatives, respectively, at 25C and 0.1 M ionic strength. The
difference in reactivity is caused by the ease of dissociation of the cyano-
bridged complexes.
While reduction of [Fe(CN)6t- by [*Ru(bipyh]2+ is diffusion con-
trolled,(34) reduction by [*Os(5-Clphenh]2+ is slower and data comparisons
lead to an estimate of the rate of electron transfer within the ion pairs of
1.6 x 10
8
s -I. Unexpectedly, this value increases with increasing ionic
strength. Reduction of [Fe(CN)6]3- by MV+ is diffusion controlled(3S) with
a rate constant of 7.6 x 10
9
M-
1
S-I at 23C, The reverse reaction involves
rate-determining successor complex dissociation and is an order of magni-
tude slower than the rate of electron transfer derived from optical data.
Solvent effects on the reaction of [Co(phenh]3+ with ferrocene in
alcohol-water mixtures cannot be explained(36) by continuum theory even
though electrostatic interactions can be ignored. Solvent effects are largest
with increasing chain size in the alcohol and microscopic changes in solvent
structure are considered important. Reaction with ferrocene(37) has enabled
an estimate to be made of the self-exchange rate for [Co(dmgh(BFht, a
clathrochelate with BF fragments capping dimethylglyoximate ligands.
The value of 1.1 x 10
2
M-
1
S-I with activation parameters I1J[t 7.3 kcal-
mol-I and as
t
-25 cal K-
1
mol-
1
in acetonitrile at 25C are similar to
T
a
b
l
e

2
.
2
.

A
s
s
o
c
i
a
t
i
o
n

a
n
d

E
l
e
c
t
r
o
n

T
r
a
n
s
f
e
r

C
o
n
s
t
a
n
t
s

f
o
r

R
e
a
c
t
i
o
n
s

b
e
t
w
e
e
n

M
e
t
a
l

C
e
n
t
e
r
s

a
t

2
5
C
,

0
.
1

M

I
o
n
i
c

S
t
r
e
n
g
t
h

K
,

k
.
h

S
y
s
t
e
m

M
-
1

s
-
1

R
e
f
.

[
C
o
(
N
H
3
)
s
p
y
]
3
+

+

[
F
e
(
C
N
)
6
t
-
2
.
4

x

1
0
3

1
.
5
1

X

1
0
-
2

2
9

[
C
o
(
N
H
3
)
6
(
3
-
C
O
N
H
2
P
y
)
]
3
+

+

[
F
e
(
C
N
)
6
t
-
2
.
5

x

1
0
3

5
.
0
4

2
9

[
C
o
(
N
H
3
)
s
(
4
-
C
O
N
H
2
P
y
)
]
3
+

+

[
F
e
(
C
N
)
6
t
-
5
.
3

x

1
0
3

3
.
5
8

2
9

[
C
o
(
N
H
3
)
s
(
4
,
4
'
_
b
i
p
y
)
]
3
+

+

[
F
e
(
C
N
)
6
t
-
2
.
3

x

1
0
3

2
.
4
0

2
9

[
C
o
(
N
H
3
)
s
(
4
-
C
H
2
C
H
2
-
4
'
-
p
y
)
]
3
+

+

[
F
e
(
C
N
)
6
t
-
2
.
8

x

1
0
3

1
.
0
1

2
9

[
C
o
(
N
H
3
)
s
(
4
,
4
'
-
N
M
e
b
i
p
y
)
]
4
+

+

[
F
e
(
C
N
)
6
t
-
3
.
2

x

1
0
3

3
.
7
4

2
9

[
C
o
(
N
H
3
)
s
(
3
-
C
N
p
y
)
f
+

+

[
F
e
(
C
N
)
6
t
-
1
.
3

x

1
0
3

3
.
4
6

X

1
0
-
1

2
9

[
C
o
(
N
H
3
)
s
(
4
-
C
N
p
y
)
]
3
+

+

[
F
e
(
C
N
)
6
t
-
2
.
5

x

1
0
3

1
.
5
1

X

1
0
-
1

2
9

[
C
o
(
N
H
3
)
s
(
3
-
C
N
p
y
)
]
3
+

+

[
F
e
(
C
N
)
6
t
'
-
1
.
5

x

1
0
3

7
.
6

X

1
0
-
1

2
9

[
C
o
(
N
H
3
)
s
(
i
m
i
d
)
f
+

+

[
(
H
2
O
)
F
e
(
C
N
l
s
]
3
-
6
7
0

1
.
6
5

x

1
0
-
1

3
2

[
C
o
(
N
H
3
)
s
N
-
p
y
-
4
C
N
]
3
+

+

[
(
H
2
O
)
F
e
(
C
N
)
s
]
3
-
5
9
7

0
.
4
6

3
3

[
C
o
(
N
H
3
)
s
N
-
p
y
-
3
C
N
]
3
+

+

[
(
H
2
O
)
F
e
(
C
N
)
s
]
3
-
7
9
9

0
.
7
1

3
3

[
C
o
(
N
H
3
)
s
(
N
C
-
4
-
p
y
)
]
3
+

+

[
(
H
2
O
)
F
e
(
C
N
)
s
f
-
2
.
2

x

1
0
6

0
.
1
6

3
3

[
C
o
(
N
H
3
)
s
(
N
C
-
3
-
p
y
)
f
+

+

[
(
H
2
O
)
F
e
(
C
N
)
s
]
3
-
2
.
3

x

1
0
6

3
.
0

X

1
0
-
3

3
3

.
.
r
:
.
.
.

<
:
:
:
>

'
"

:
:
:
,

'
"
'

5
'
-
;
:
:

'
"

<
:
)
-
'
"

'
"

'
"

;
:
:

9

3

"
=
I

>
<

'
"

'
"

[
*
O
s
(
5
-
C
l
p
h
e
n
h
]
2
+

+

[
F
e
(
C
N
l
6
t
-
[
C
o
(
N
H
3
l
s
0
2
C
C
H
(
O
H
l
C
H
3
]
2
+

+

C
e
4
+

3
6

[
C
o
(
N
H
3
l
s
O
C
C
H
(
O
H
l
P
h
f
+

+

C
e
4
+

4
.
0

x

1
0
2

[
C
o
(
N
H
3
l
s
0
2
C
C
(
O
H
l
P
h
2
f
+

+

C
e
4
+

4
.
9

x

1
0
2

[
M
0
2
0
4
(
R
,

S
p
a
d
a
f
-
+

[
(
e
n
h
C
o
(
I
L
N
H
2
I
L
0
2
l
C
o
(
e
n
h
t
+

5
1

[
C
o
(
N
H
3
l
s
(
3
-
p
y
o
A
c
l
R
u
(
N
H
3
l
4
H
2
0
t
+

[
C
o
(
N
H
3
l
s
(
4
-
p
y
o
A
c
l
R
u
(
N
H
3
l
4
H
2
0
]
4
+

[
C
o
(
N
H
3
l
s
(
n
i
c
o
t
i
n
a
t
e
l
R
u
(
N
H
3
l
4
H
2
0
t
+

[
C
o
(
N
H
3
l
s
(
i
s
o
n
i
c
o
t
i
n
a
t
e
l
R
u
(
N
H
3
l
4
H
2
0
t
+

[
C
o
(
N
H
3
l
s
(
3
-
c
i
n
c
h
o
n
m
e
r
o
n
a
t
e
l
R
u
(
N
H
3
l
4
H
2
0
]
3
+

[
C
o
(
N
H
3
l
s
(
3
-
c
i
n
c
h
o
n
o
m
e
r
o
n
a
t
e

H
)
R
u
(
N
H
3
l
4
H
2
0
t
+

[
C
o
(
N
H
3
l
s
(
4
-
c
i
n
c
h
o
n
m
e
r
o
n
a
t
e
l
R
u
(
N
H
3
l
4
H
2
0
]
3
+

[
C
o
(
N
H
3
l
s
(
4
-
c
i
n
c
h
o
n
m
e
r
o
n
a
t
e

H
l
R
u
(
N
H
3
l
4
H
2
0
t
+

[
C
o
(
N
H
3
l
s
(
4
-
c
i
n
c
h
o
n
m
e
r
o
n
a
t
e

H
l
R
u
(
N
H
3
l
4
S
0
4
]
2
+

[
C
o
(
N
H
3
l
s
(
4
-
c
i
n
c
h
o
n
m
e
r
o
n
a
t
e

H
l
R
u
(
N
H
3
l
4
I
]
3
+

[
C
o
(
N
H
3
l
s
(
4
,
4
'
-
b
i
p
y
l
R
u
(
N
H
3
l
4
S
0
3
]
3
+

[
C
o
(
N
H
3
l
s
(
p
y
r
a
z
i
n
e
l
R
u
(
N
H
3
l
4
S
0
3
]
3
+

[
(
N
H
3
l
s
R
u
S
2
C
s
H
g
R
u
(
N
H
3
l
s
]
5
+

[
(
N
H
3
l
5
R
u
S
2
C
g
H

1
2
R
u
(
N
H
3
l
s
]
5
+

[
(
N
H
3
l
5
R
u
S
2
C
l
l
H
1
6
R
u
(
N
H
3
l
s
]
s
+

1
.
6

x

1
0
9

2
.
7

x

1
0
-
3

3
.
6

X

1
0
-
3

1
.
0
7

X

1
0
-
3

0
.
7
6

5
.
6
6

x

1
0
-
4

7
.
8
3

X

1
0
-
3

1
.
8
0

x

1
0
-
3

1
.
2
4

x

1
0
-
2

2
.
5
7

x

1
0
-
3

1
.
1

X

1
0
-
3

3
.
4

x

1
0
-
2

4
.
2

X

1
0
-
2

5

0
.
5

4

X

1
0
-
4

0
.
1
2
8

8
.
0

X

1
0
7

4
.
9

X

1
0
6

3
.
5

X

1
0
4

3
4

4
8

4
8

4
8

7
1

7
9

7
9

7
9

7
9

7
9

7
9

7
9

7
9

7
9

7
9

7
9

7
9

8
0

8
0

8
0

-
I
:
:
.
.

;
:
s

0
:
:
:
:
:
,

-
I
:
:
.
.

.
.
.
.
.
.

42 2 Reactions between Metal Complexes
those for [Co(phenh]3+/2+. Ferricinium ion has been used(38) to probe the
reactivity of horse heart cytochrome c and Marcus correlations reveal the
importance of hydrophobic 7T-conducting ligands in reactions with proteins.
Self-exchange rates of the [bis(T/2-arene)CrtIO reaction have been
examined(39) by esr line broadening in DMSO. As with ferrocene, work
terms can be ignored and internal contributions to the activation free energy
calculated. The solvent dependence and thermodynamic parameters are in
reasonable agreement with Marcus predictions using a dielectric continuum
model though microscopic reactant-solvent interactions in forming the
encounter complex cannot be accounted for. Problems with steric and
non-adiabatic factors are also prevalent.
2.5. Cobalt(II)
Oxidations(4o) of a number of cobalt and nickel macro cyclic complexes,
and others, by [Co(H
2
0)6]3+ have been examined and though Marcus
correlations are good, the evaluated self-exchange rate, 10-
12
M-
1
s -\ is
very much lower than the measured rate of 5 M-
1
s -1. This is similar to
the [Co(NH
3
)6]3+/2+ case where Frank-Condon restrictions are important.
The very low Marcus-derived rate involves some nonadiabatic character
and the rapid measured self-exchange rate is explained in terms of a
water-bridged inner-sphere pathway. The difficulty in forming H
2
0+ pre-
cludes such a pathway in reactions of weaker oxidants.
A cyanide-bridged dead-end complex is formed between [Co(edta)]2-
and [Fe(CN)6]3- and electron transfer takes place by an outer-sphere
mechanism(41) with a rate constant of 2.61M-
1
s-
1
at 25C and 0.26M
ionic strength. A pKa for [Co(edta)]2- of 13.91 suggests a species
[Co( edta)OH]3- which reacts with a rate constant of 6.84 M-
1
s -1. The
rate difference has been used to calculate a potential for [Co(edta)OHf-
/2
-
of 0.32 V.
In acidic media, the lL-oXO dimer [{(H
2
0)Co[14 ]aneN
4
h0 2t+ shows(42)
properties of both an oxidant and a reductant. The reactions have first-order
limiting rate laws with the same limiting rate of 0.57 S-l at 25C and 0.1 M
ionic strength and a mechanism involving cleavage of a Co-O bond to give
[Co([14 ]aneN
4
) (H
2
0)z]2+ and [Co([14 ]aneN
4
)(H
2
0)02f+' respectively,
a reductant and an oxidant. Reductions of [Co([14]aneN
4
)(H
2
0)02f+ by
Fe
2
+ or Cr
2
+ can be inner sphere but have not been examined in detail.
There is evidence that inner-sphere pathways are involved in the self-
decomposition of the complex.
Crystal structure analysis(43) of cobalt(II) and cobalt(III) trans-diaquo
macrocycles show variations only in the CO-OH2 bond lengths and allow
2.6 Nickel(II) and (III) 43
correlations to be drawn between the experimental self -exchange rates and
calculated reorganizational energy. Calculated values are consistently
10 kcal mor
1
lower than the experimental values and the difference is
ascribed to an electron exchange term.
Direct measurement of Co(III)/(II)(TPP) self-exchange has been
possible(44.4S) using nmr in CDCh solution in the presence of pyridine. The
main cobalt(III) species is the Cn ion pair and the
outer-sphere self-exchange rates increase by almost three orders of magni-
tude on going from [Co(II)(TPP)] to [Co(II)(TPP)(py)]. The correspond-
ing cobalt(III) halide complexes [Co(III)(TPP)X], where the halide is now
metal bound,(46) react much more quickly by an inner-sphere pathway and
show the normal order r > Br - > Cl- for bound halide.
An outer-sphere electron transfer(47) is the initial step in reactions of
[IrCI
6
]2- and [Fe(bipyh]3+ with methyl and ethyl-cobalt(III) macrocycles
in acetonitrite solution. The organic ligand is labilized as a radical which
is subject to dimerization or further reactions with the oxidant.
A cerium(IV)-cobalt(III) intermediate is detected in the oxidation(49)
of [(NH3hCo(III)(a-hydroxyacid)] with Ce(IV) to give Ce(III), Co(1I) ,
CO
2
, and the corresponding ketone. There is no evidence for a coordinated
radical, and electron transfers to Ce(IV) and Co(lll) may be nearly syn-
chronous with C-C bond scission. Similar oxidation by Tl(III), which acts
as a two-electron donor, results in no cobalt(lI) formation.
Methylcobalamin, CH
3
B12, reacts with [AuC4r and [AuBr4r accord-
ing to a rate law suggesting(49) outer-sphere complex formation followed
by electron transfer with association constants, 630 M-
1
and 860 M-
1
, and
rate constants 1.0 x 10-
2
and 4.8 x 10-
3
s -t, respectively at 23C and 1.0 M
ionic strength. Subsequent to the electron transfer, the methylcobalamin is
hydrolyzed to aquocobalamin and "Au(II)" produced is thought to oxidize
the corrin ring giving colloidal gold and an overall 1 : 2 ([AuCI
4
r: CH3Bd
stoichiometry.
2.6. Nickel(II) and (III)
[Ni(II)([14]aneN
4
)]2+ is oxidized by CoOH
2
+ with a rate constant of
4.7 x lOS M-
1
S-l in 1.0M perchlorate media.(SO) Sulfate, which has no
effect on the ratio, complexes strongly with the nickel(lI) reaction product.
The effects of sulfate, phosphate, and chloride ions on the decomposition
reactions of a nickel(III)-macrocycle have been investigated.(Sl) Anion
coordination prevents proton abstraction from the macrocycle, the probable
decay mechanism, and stabilizes the nickel(III) complex. Similar con-
clusions are reached in a study of the Br2"(S2) and (SCN) 2" (S3) oxidations of
44
2
pyridine-based macrocyclic complexes (2). The reaction products are anion
coordinated with stability constants of 360 M-
1
and _10
4
M-
1
for mono-
bromo and thiocyanato complexes, respectively. The former complex
[Ni2Br(H
2
0)] reacts with Fe
2
+ with a rate constant of 1.2 x 10
4
M- S-1
extrapolated to zero ionic strength. Unsaturated derivatives of the
macrocyclic ligand have also been examined(53,54) and, in reaction with 'OH
radical, coordinated ligand radicals can be formed in preference to
nickel(III), depending on the degree of unsaturation and consequently,
axial solvation. Radical anions such as Brl" are, however, particularly
effective in removing an electron from the metal center.(55,56)
A variety of nickel(III) macrocycles(57) and phenantholine(58) deriva-
tives have been characterized. Pulse radiolysis studies(59) on
[Pt(NH
3
)4(OHht and [Pt(NH
3
MH
z
O)(OH)f+ have also been reported.
2.7. Copper(I) and (II)
Reduction of the copper(II) complex of 4,7-diphenylsulphonated-2,9-
dimethylphenatholine, [Cu(dpmph]2-, by excess [Fe(CN)6t- at pH 8.0
reveals(60) limiting rate behavior which is interpreted in terms of a 5 to 4
coordination change in the complex as shown in equation (2), with a rate
constant of 229 S-1 at 25C. The four-coordinate complex has then little
barrier to reduction. Different limiting rates are found(61) with a variety of
other reduct ants, Red, and a further pathway shown in equation (3) involv-
ing direct reduction of the five-coordinate species is required to explain
the data. This reduces the rate for the 5 to 4 coordination change to 135 s -1.
[Cu(dpmp)zOH
2
]2- [Cu(dpmp)z]2- + H
2
0 (2)
[Cu(dpmphOH
2
f- + Red [Cu(dpmph]3- + H
2
0 + Ox (3)
It is of interest to note that reduction(62) of copper(II) N
4
-macrocyclic
complexes by CO; radical results in planar N
4
-copper(I) species which
2.8 Molybdenum(IV) and (V) 45
rearrange with rate constants ranging from 5 x 10
2
to 3.6 X 10
4
S-1 to give
tetrahedral complexes which undergo dissociation.
With copper(II) S4-macrocycles and chelating ligands, there is no
abnormally low barrier to electron transfer in reaction with cytochrome
c(II), which suggests(63) that there is no appreciable rate enhancement due
to the thioether linkage. Oxidations of cytochrome c(II) by Cu
2
+ and CuCl+
have also been examined.(64) The Cu2+ ion binds(65) to the protein but this
bound copper is not involved in electron transfer.
Electron transfer quenching of [*Cu(dmpht by [Co(enh(bipy)f+,
trans-[Co(NH3McNht and cis-[Co(idahr is close to the diffusion-
controlled limit. (66) This is much faster than' reaction with [Co(NH
3
)6]3+.
The self-exchange rate for the copper(III)/{II)-tripeptite complex,
[Cu(H-
2
Aib
3
)]o/-, where Aib is a-aminobutyric acid, has been examined(67)
using nmr techniques. The rate constant, 5.5 x 10
4
M-
1
S-1 is virtually
independent of pH and increases only by 12%-16% on a ten-fold increase
in [Cn, which rules against an inner-sphere bridging mechanism. Consider-
ation of the tlS* suggests that a bridging H
2
0 molecule is a possibility, but
an alternative outer-sphere mechanism where both copper(III) and
copper(II) complexes are five-coordinate in the transition state is equally
consistent.
The implication of this result is considered(68) for reaction of [IrCI
6
]2-
with a series of copper(II) peptides where rates were measured using pulsed
flow. The rate data fit a good Marcus plot with a predicted copper(III)/(II)
self-exchange rate >10
8
M-
1
S-1 and an alternative inner-sphere chloride
bridged mechanism is considered to operate. This is also in agreement with
the observation that at very high driving forces, the rate is independent of
the driving force, and the limiting rate, slower than diffusion controlled, is
the formation of the [IrCI
6
f--copper(II)-peptide bridge. Electron transfer
data for a copper(II) macro cyclic peptide complex have also been
reported. (69)
2.B. Molybdenum(IV) and (V)
Oxidations of the molybdenum(IV) trimer M0
3
0!+ by [IrCI
6
]2- and
[Fe(phenh]3+ are inhibited by H+ indicating initial proton dissociation from
the molybdenum complex.(70) No mixed-valence species are detected and
the product with [Fe(phenh]3+ is Mo(VI), while with [IrCI
6
f-, Mo(V) is
produced. The difference is accounted for in terms of an inner-sphere
mechanism for the latter reagent. Activation parameters are similar to
those of substitution of SCN- or M030!+.
When the complexes [Mo(Vh04(R, Spada)f- and
(p,NH2' O;:)Co(III)(en)z] are mixed(7!) in a 1 : 1 ratio, only half of the Mo(V)
is oxidized to Mo(VI), and the Mo(V) remaining shows an enantiomeric
excess of the R-pada isomer. This excess increases from 0.15% to 0.25%
on increasing the ionic strength from 0.2 M to 2.0 M. At pH 3.5, and 25C,
the kinetics of the reaction indicate complex association with K = 51 M-
1
followed by electron transfer, k = 0.76 s-t, at 0.2M ionic strength and
these respectively decrease and increase with increasing ionic strength. The
differing stereoselectivities are explained by different stereo selectivities in
the association and electron transfer steps.
Disproportionation(72) of the complex [Mo(Vh03(S2CSCH(CH3)z)4]
to monomeric Mo(IV) and Mo(VI) species takes place at 12.2 S-1 in 1,2-
dichlorethane. The Mo(VI) product slowly undergoes an internal redox
reaction to give a Mo(V) dimer and disulfide.
2.9. Ruthenium(II)
Oxidation of [Ru(bipyh(py)OH
2
f+ occurs(73) in two one-electron steps
giving firstly [Ru(bipyh(py)OH]2+ and then [Ru(bipyh(py)O]2+. Examin-
ation of the comproportionation (4) which has an equilibrium constant,
kd kb' of 72 yields(76) a pH-independent rate constant of 2.10 x 105 M-
1
S-1
for kf at 2S.3C and 0.1 M ionic strength. This comparatively low electron
transfer rate shows a large deuterium isotope effect kH
2
0/ k
D20
= 16.4,
indicating a coupled proton transfer. The reaction may be considered a
hydrogen atom transfer.
[Ru(bipyh(py)OH
2
f+ + [Ru(bipy)z(py)Of+ [Ru(bipy)z(py)OH]2+
(4)
Outer-sphere reductions by [Ru(NH
3
)6]2+ and [Ru(NH
3
)s(H
2
0)f+ are
proposed in reactions with cobalt(III) oxalate(7S) and ruthenium(III) oxalate
and acetate complexes. (76) Both protonated and unprotonated monodentate
oxalate complexes are reactive.
Line broadening in nmr experiments has been used to determine(77)
self-exchange rates for [Ru(4,4'-Me2bipy)(hfac)2tIO, [Ru(4,4'-Me2bipy)-
(acacht
l
- and [Ru(hfachr
/o
in acetonitrite solution. The reactions are
outer-sphere in nature and vary with solvent dielectric according to Marcus
expectations.
Determination(78) of the molecular structures of [Ru(NH
3
)spyrazine]2+
and [Ru(NH
3
)spyrazine]3+ has allowed a model of the
[Ru(NH
3
)spyrazine Ru(NH
3
)5]S+ mixed-valence ion to be constructed. The
47
delocalization energy is 0.4 e V and it is concluded that in a medium with
sufficiently high dielectric, the complex could have properties of a localized
mixed-valence ion.
Addition of reductant to complexes of the type [(H20)-
(NH
3
)4Ru(III)RCo(III)(NH
3
)s]4+ produces the corresponding
ruthenium(II) complex and allows examination of the rate of intramolecular
electron transfer from ruthenium to cobalt. (79) With a series of pyridineace-
tate bridging groups R, the electron transfer rates vary little with bridge
structure and are considered to be close to adiabatic in nature. However,
the corresponding sulfite-bound ruthenium complex [(S03)-
(NH3)4Ru(4,4'-bipy)Co(NH3)s]3+ shows an anomalously low rate of 4 x
10-
4
S -1 compared with the more normal rate of 0.128 s -1 for the pyrazine-
bridged species, and may be nonadiabatic.
Intervalence transfer bands have been noted(80) in a series of saturated
spiro sulfur-bound ruthenium(III)(II) mixed-valence dimers [(NH
3
)sRuS
C2n+2H4nS Ru(NH
3
)s]s+, where n = 2,3, or 4 indicates the number of spiro
rings. Calculated electron transfer rates decrease with intermetal distances
giving values of 8.0 x 10
7
S -1 at 11.3 A for n = 2, 4.9 X 10
6
s -1 at 14.4 A
for n = 3, and 3.5 x 10
4
S-1 at 17.6 A for n = 4 indicating very effective
tunneling even at 17.6 A with only a O'-bonded framework.
Data from the [*Ru(bipyhf+ reduction of lL-superoxo-dicobalt(III)
species have been used(81) to determine self-exchange rate constants using
Marcus theory. The rates vary from 1.3 x 10-
7
M-
1
S-1 for
[(NH
3
)4CO(IL02, NH
2
)Co(NH
3
)4]3+ to 3.2 X 10
4
M-
1
S-1 for
[(phen)zCo(IL02, NH
2
)Co(phen)z]3+, and it is thought that the very low
value for NH3 and en complexes(82) indicates involvement of a proton in
the redox process. Examination of the rate of electron transfer quenching
of [*Ru(bipyh]2+ presents problems if the quencher absorbs, and novel
technique must be applied. Quenching by [Co(phenh]3+ by an electron
transfer mechanism accounts for 52%-56% of the total quench rate.(83)
Comparisons of the reduction of [Co(NH
3
)sLr+ complexes, where L
is a substituted pyridine ligand, by [*Ru(bipyh]2+(84) and MV+(8S) leads to
some conclusions concerning the chemical mechanism which is thought to
operate in the [*Ru(bipyhf+ case. Rates for MV+ reactions are an order
of magnitude smaller with L = pyridine and 1,2-bis(4-pyridyl)ethane than
they are with 4,4' -bipy and its N -methylated derivative consistent
with direct reduction of the cobalt center in the former case (kRul k
Mv
+ =
11-14) where production of coordinated radicals is thermodynamically
unfavorable. The faster reactions are diagnostic of heterocycle reduction
(kRu/ k
MV
+ = 3-6).
Ascorbate reduction(86) of [*Ru(bipyhf+ gives [Ru(bipyht, which
can be used to reduce [Co(phenhf+ to the blue [Co(phen)nt ion. This ion
reacts in aqueous medium to give a hydride intermediate in the generation
of H2 gas. Electron transfer quenching by [Rh(bipyh]3+ yields [Rh(biPY)n]2+
species(87) which disproportionate to give a rhodium(I) complex. In the
presence of platinum, this rhodium species will also react to give H2 gas.
Some of the redox and substitution characteristics(88) of [Rh(bipyh]2+
and [Rh(bipyht and the mechanism of H2 production by [Rh(bipyht
involving formation of a hydride species [Rh(bipy)zH]2+ which is reduced
by [Rh(bipyh]2+ to give the direct precursor to H2 formation have been
reported. (89)
The usefulness of [*Ru(bipyhf+ in elucidating the chemistry of highly
reducing species is highlighted in a paper(90) dealing with the [Rh( 4,4'-
Me2bipyh]3+ system. This shows good Marcus behavior in reactions with
a number of excited-state ruthenium species and has a reduction potential
of -0.97 Y with a self-exchange rate of 2 x 10
9
M-
1
S-I. The osmium
complexes [Os(III)/(II)(NH3)5X], where X is Cl-, Br-, r, H
2
0, NH
3
, or
N
2
, all have self-exchange rates in the range 10
2
_10
5
M-
1
S-I.
Photolysis(91) of the ion pair {(NH
3
)Rucf+ leads to reduc-
tion of the amine complex which rapidly hydrolyzes. A further inner-sphere
electron transfer gives the bridged product [(NH
3
)sRu(III)NCRu(II)-
(CN)s].
A large number of papers dealing with water-splitting reactions involv-
ing mainly the effects of catalysts on the [*Ru(bipyhf+ /(My
2
+) system
have appeared. (92-98)
2.11. Europium (II)
An ac voltametric method has been exploited(99) to determine rates
of a number of Eu
2
+ reductions of cobalt(III) complexes with half-lives in
the range 10-
2
-1 s. The rate data show good agreement with conventional
determinations. Reductions(100) of cobalt(III) complexes,
[Co(NH3)s02CLpy]2+, where -02CLpy is a nicotinamide or
isonicotinamide derivative, by Cr
2
+ and Eu
2
+ are sensitive to the distances
between the pyridine ring and the carboxylate-bound cobalt. However,
reactions with y2+ are insensitive and are limited by substitution at that
metal ion. Effects of charge have been studied(1Ol) on Cr
2
+, y2+, Eu
2
+, and
de hydro flavin reductions of a number of [Co(NH
3
)sL]3+or2+ complexes
where L has similar structure but different charge. The neutral reductant
2.13 Metalloprotein Studies 49
shows no trends but the higher positive charge retards the reactions of the
metal ion reductants.
Production of H2 from water by photolysis of the iridium hydride
complex [HlrCI
6
]2- is reported(102) and the facility of using cluster com-
pounds is discussed. The excited state of [M0
6
Ch4]2- has a relatively long
lifetime(103) in CH
3
CN and will reduce electron acceptors such as MV
2
+
with a reduction potential of -0.4 V. The 88* excited state of [Re
2
CI
s
]2-
is a strong oxidant(104) and gives a facile route to the powerful reductant
[Re2CIsr. while near-diffusion-controlled oxidative quenching reactions
of [*Ph(P
2
0
s
)4H
s
t-, which is a stronger reducing agent than
[*Ru(bipy h]2+, have been reported. (105)
2.13. Metalloprotein Studies
Oxidation and reduction (1 06) of cytochrome c at a gold electrode,
modified by treatment with 4,4'-bipy, is close to reversible but shows
additional potential-independent processes before and after the electron
transfer. Absorption of the protein on the electrode surface takes place to
allow rapid electron transfer and it is suggested that the heme edge is
oriented to the surface.
At low pH, horse heart cytochrome c(II) has a pKa of 3.1, which may
be due(107) to protonation of histidine 26, causing a small conformational
change at the heme region increasing surface exposure. This increases the
rate of oxidation by [Ru(NH
3
)spy]3+ from 6.0 x 10
3
to 3.77 X 10
4
M-
1
S-1
in 0.1 M acetate at 25C, Table 2.3. The behavior differs from previous
studies(1OS) in this pH range.
A reexamination(109) of the reduction of cytochrome c(I1I) by
[Fe(CN)6t- and related reagents has shown that any association prior to
electron transfer must be weak withK < 200 M-
1
at 0.10 M ionic strength.
Similar conclusions are reached about oxidation of cytochrome c(I1) by
[Fe(CN)6]3-.
Modified cytochrome c(I1) and (III) proteins with lysine-bound 4-
carboxy-2,6-dinitrophenyl groups have been used(llO) to map the site of
electron transfer. With negatively charged inorganic partners there is a
factor of 2 decrease in rate or modification of lysine 72 and 13 and a
comparable increase for positively charged reagents, showing that the
inorganic complexes transfer electrons at the exposed heme edge.
The active site of cytochrome c, a heme-octapeptide, has been iso-
lated(111) and electron transfer reactions with [*Ru(bipyhf+ examined. The
T
a
b
l
e

2
.
3
.

R
a
t
e

C
o
n
s
t
a
n
t
s

a
n
d

T
h
e
r
m
o
d
y
n
a
m
i
c

P
a
r
a
m
e
t
e
r
s

f
o
r

M
e
t
a
l
l
o
p
r
o
t
e
i
n

R
e
a
c
t
i
o
n
s

a
t

2
5
C

/
1
-
,

R
e
a
c
t
i
o
n

M

c
y
t

c
(
1
l
)

+

[
R
u
(
N
H
3
)
s
p
y
]
3
+

0
.
1

c
y
t

c
(
1
l
)

H

+

[
R
u
(
N
H
3
)
s
p
y
]
3
+

0
.
1

c
y
t

c
(
I
I
I
)

+

[
F
e
(
C
N
)
6
t
-
(
p
H

7
.
2
)

0
.
1

c
y
t

c
(
I
I
I
)

+

[
F
e
(
C
N
l
s
4
-
N
H
2
P
y
]
3
-
0
.
1

c
y
t

2
(
I
I
I
)

+

[
F
e
(
C
N
)
s
i
m
i
d
]
3
-
0
.
1

c
y
t

c
(
1
l
)

+

[
F
e
(
C
N
)
6
]
3
-
0
.
1

c
y
t

c
(
1
l
)

+

[
F
e
(
C
N
)
s
(
N
C
S
)
]
3
-
0
.
1

c
y
t

c
(
1
l
)

+

[
F
e
(
C
N
)
s
(
4
-
N
H
2
P
y
)
]
2
-
(
p
H

9
.
4
)

0
.
1

c
y
t

c
(
1
l
)

+

[
F
e
(
C
N
)
s
(
N
H
3
)
]
2
-
0
.
1

c
y
t

b
s
(
I
I
I
)

+

[
F
e
(
E
D
T
A
)
]
2
-
0
.
5

c
y
t

b
s
(
I
1
l
)

H

+

[
F
e
(
E
D
T
A
)
f
-
0
.
5

c
y
t

c
(
I
I
I
)

d

+

[
F
e
(
E
D
T
A
)
f
-
0
.
3

c
y
t

c

d
(
I
1
l
)

+

[
F
e
(
E
D
T
A
)
]
2
-
0
.
3

H
I
P
I
P
(
r
)

+

[
C
o
(
4
,
7
-
d
i
p
h
e
n
y
l

s
u
l
f
o
n
a
t
e

p
h
e
n
h
]
3
-
0
.
1

(
p
H

7
.
0
)

H
I
P
I
P
(
r
)

+

[
M
n
(
C
y
D
T
A
)
(
H
2
0
)
r

0
.
1

H
I
P
I
P
(
o
)

+

[
F
e
(
C
N
)
6
t
-
0
.
1

P
h
a
s
e
o
l
u
s

v
u
l
g
a
r
i
s

P
l
a
s
t
o
c
y
a
n
i
n

+

[
*
R
u
(
b
i
p
y
h
f
+

0
.
1

R
h
u
s

v
e
r
n
i
c
i
f
e
r
a

S
t
e
l
l
a
c
y
a
n
i
n

+

[
*
R
u
(
b
i
p
y
h
f
+

0
.
1

P
s
.

a
e
r
u
g
i
n
o
s
a

A
z
u
r
i
n

+

[
*
R
u
(
b
i
p
y
h
f
+

0
.
1

k
,

M
-
1
s
-
1

6
.
0

x

1
0
3

3
.
7
7

x

1
0
4

3
.
5

x

1
0
4

6
.
7

x

l
O
s

4
.
2

x

l
O
s

9
.
1

x

1
0
6

1
.
3

x

1
0
6

3
.
8

x

1
0
6

2
.
7
5

x

1
0
6

2
.
5

x

1
0
2

7
.
2

x

1
0
2

1
.
9

x

1
0
2

1
.
0
4

x

1
0
2

6
8

1
.
2
6

x

1
0
3

2
.
4

x

1
0
2

1
.
6

x

1
0
9

4
.
2

x

1
0
8

6
.
9

x

1
0
8

i
l
H
'
,

k
c
a
l

m
o
l
-
1

5
.
4

7
.
0

3
.
6

i
l
S
'
,

c
a
l

K
-
1

m
o
l
-
1

-
2
9

-
2
6
.
9

-
2
7
.
7

R
e
f
.

1
0
7

1
0
7

1
0
9

1
0
9

1
0
9

1
0
9

1
0
9

1
0
9

1
0
9

1
1
2

1
1
2

1
1
3

'
"

1
1
3

!
:
l

'
"
'

1
1
5

g
"

;
:
:

'
"

1
1
5

0
-
'
"

1
1
5

?

'
"

1
1
7

'
"

;
:
:

1
1
7

1
1
7

e
:

g

3

'
<
:
l

'
"

>
<

'
"

'
"

2.13 Metalloprotein Studies 51
self-exchange rate is >10
6
M-
1
S-1 at 25C and 0.1 M ionic strength,
substantially higher than the 1.2 x 10
3
M-
1
S -1 exchange rate of the parent
protein, and though consistent with the idea that it is more accessible it is
suggested that reorganization of the native protein may retard electron
transfer.
Electron transfer reactions of cytochrome b
s
(II1) with [Fe(edta)]2-
have been examined.(112) A pKa of 5.85 is detected with a small decrease
in reactivity to higher pH which may be due to a shift in reduction potential
or to electrostatic effects. The exchange and activation parameters are
consistent with heme edge electron transfer.
Multiphasic kinetics are observed(113) in the corresponding reduction
of cytochrome cd, (111)(111), which has two type c and two type d
1
heme
groups. Reaction with heme c is first order in both protein and reductant
and is close in rate to reaction of one of the heme d groups. However, the
second heme d group is reduced intramolecularly from heme c with a rate
constant of 0.31 S-1. The reactivity of the protein is lower than that of
cytochrome c, reflecting deeper burying of the active sites.
A caveat on the use of pulse radiolysis for the study of metalloproteins
has appearedY
14
) While the 2Fe-2S feredoxin is cleanly reduced by
with 8Fe-8S systems and especially with H1P1P from Chromatium v where
the active site is buried, the efficiency of metal site reduction is as low as
50%.
A number of different binding sites for metal ion complexes on
oxidized and reduced forms of H1P1P are implicated(11S) from reactions
with [Co(4,7-diphenylsulfonatephenh]3-, [Mn(CyDTA)(H
2
0)]-, and
[Fe(CN)6]3-. Evidence for binding is found only with the first reagent but
competition studies reveal no effect of binding of the cobalt complex on
the reaction of [Mn(CyDTA)(H
2
0)r and [Fe(CN)6]3-. Reaction of the
cobalt complex is affected by protonation of histidine 42, but it is suggested
that the closest approach to the H1P1P center at the hydrophobic surface,
threonine-81 and phenyl-alanine-48, is a preferable site for electron trans-
fer. Other studies(116) are in general agreement with this suggestion.
Rates of electron transfer from [*Ru(bipyh]2+ to copper blue proteins
have been reported.(l17) With plastocyanin from Phaseolus vulgaris, the
reaction is close to the diffusion limit, indicating very close approach of
the two metal centers.
Chromium(lI) reduction of Ps. aeruginosa azurin gives a protein-bound
chromium(II1) product which has been subjected to proteolytic diges-
tion.(118) It is suggested that the metal ion is coordinated to lysine-85 and
glutamine-91 thereby outlining an electron transfer pathway through his-
tidines 35 and 46 in the protein.
Chapter 3
Metal-Ligand Redox
Reactions
3.1. Introduction
In preparing this chapter, I felt that it might be worthwhile to consider the
reactivity of the nonmetallic substrate as a dominant force in the determina-
tion of the mechanism. Accordingly I have arranged the chapter with
subheadings collecting the reactions of like substrates together. This departs
from the order used in previous volumes and I hope that the readers are
not too inconvenienced. Where possible, collections of data have been
tabulated.
3.2. Ascorbic Acid H2A
Reduction of chromic acid by ascorbic acid proceeds(1) in a two-
electron step [equation (1)] with a rate constant of 1.5 x 10
4
M-
1
S-1. The
H2A + H2Cr04 ...... A' + Cr(IV) (1)
low entropy of activation (Table 3.1) is consistent with direct formation of
dehydroascorbic acid, A'. In the reduction (2) of another potential two-
electron oxidant, the nickel(IV) oxime-imine complex [NiL]2+, detection
of a nickel(11I) intermediate confirms consecutive one-electron transfers
and participation of ascorbate radicals. Ascorbate ion is the sole reductant
and the low substitution lability of [NiL]2+ suggests that an outer-sphere
53
T
a
b
l
e

3
.
1
.

R
a
t
e

C
o
n
s
t
a
n
t
s

a
n
d

T
h
e
r
m
o
d
y
n
a
m
i
c

P
a
r
a
m
e
t
e
r
s

f
o
r

A
s
c
o
r
b
i
c

A
c
i
d

R
e
d
u
c
t
i
o
n

a
t

2
5

/
J
-
,

k
,

t
:
.
H
*
,

t
:
.
S
*
,

M

M
-
t
s
-
t

k
c
a
l
m
o
l
-
t

c
a
l

K
-
t

m
o
l
-
t

R
e
f
.

R
e
d
u
c
t
a
n
t
:

H
2
A

H
2
C
r
0
4

0
.
5

1
.
5

x

1
0
4

7

-
1
7

1

[
C
o
(
o
x
h
J
3
-
1
.
0

1
.
2

X

1
0
-
4

2
6

U

5

[
F
e
(
p
h
e
n
h
J
3
+

1
.
0

1
.
7
3

x

1
0
5

5

-
1
7

3

R
e
d
u
c
t
a
n
t
:

H
A

-
[
N
i
L
H
J
2
+

0
.
1

3
.
0
2

x

1
0
5

2

[
N
i
L
J
+

0
.
1

1
.
3
6

x

1
0
4

2

[
C
o
(
p
h
e
n
h
J
3
+

0
.
1

0
.
4
0

1
1

-
2
2

3

[
C
o
(
b
i
p
y
h
J
3
+

0
.
1

0
.
1
3

9

-
3
3

3

[
C
o
(
M
e
6
[
1
4
J
4
,
1
1
-
d
i
e
n
e
N
4
)
(
O
H
2
h
J
3
+

0
.
1

3
.
4

4

[
C
o
(
M
e
6
[
1
4
J
4
,
1
1
-
d
i
e
n
e
N
4
)
(
O
H
2
)
O
H
f
+

0
.
1

1
.
1

x

1
0
2

4

[
C
O
(
M
e
4
[

1
4
J
t
e
t
r
a
e
n
e
N
4
)
(
O
H
2
h
J
3
+

0
.
1

4
.
2

x

1
0

4

[
C
O
(
M
e
4
[
1
4
J
t
e
t
r
a
e
n
e
N
4
)
(
0

H
2
)
(
O
H
)
f
+

0
.
1

1
.
3

x

1
0
3

4

[
C
o
(
m
s
-
M
e
6
[
1
4
J
a
n
e
N
4
)
(
O
H
2
h
J
3
+

0
.
1

4
.
2

x

1
0

4

[
C
o
(
m
s
-
M
e
6
[
1
4
J
a
n
e
N
4
)
(
O
H
2
)
(
O
H
)
]
2
+

0
.
1

5
.
5

x

1
0

4

S

[
C
o
(
[
1
4
J
a
n
e
N
4
)
(
O
H
2
)
(
O
H
)
f
+

0
.
1

2
.
9

x

1
0

4

I
"

[
C
o
(
o
x
h
J
3
-
1
.
0

4
.
1

X

1
0
-
3

1
3

-
2
6

5

r
-
[
F
e
(
p
h
e
n
h
J
3
+

1
.
0

6
.
4
5

x

1
0
8

2

-
1
2

5

;
:
:
,
:

[
*
R
u
(
b
i
p
y
h
f
+

2

X

1
0
7

1
2

$
:
)
.
.

:
:
t
I

R
e
d
u
c
t
a
n
t
:

A

2
-
'
"

[
C
o
(
p
h
e
n
h
]
3
+

0
.
1

5
.
8

x

1
0
6

2
6
a

_
U
a

3

l
o
(

:
:
t
I

[
C
o
(
b
i
p
y
h
J
3
+

0
.
1

2
.
1

x

1
0
6

1
9
a

-
3
8
a

3

'
"

s
:
:
.

[
C
o
(
e
n
)
(
p
h
e
n
h
J
3
+

0
.
1

1
.
0

x

1
0
6

3

.
.
.
,

5

;
:
:
,
:

"
"

a

I
n
c
l
u
d
e
s

p
K
.

p
a
r
a
m
e
t
e
r
s
.

3.3 Quinols and Catechols
55
mechanism is operating. Studies with optically active solutions of nickel(IV)
show no chiral discrimination in the oxidation of L-ascorbate.
Outer-sphere reductions of [Co(phenh]3+, [Co(bipyh]3+, and
[Coen(phen)z]3+ by ascorbate ion have been examined(3) and though reac-
tions with the ascorbate dianion participate in all three cases,
[Coen(phen)z]3+ does not react with HA -. Calculations based on the Marcus
relationship and using a potential of 0.88 V for the HA IHA - couple allow
good agreement with the experimental results. With cobalt(III) trans-
diaquo-N
4
-macrocyclic reagents, agreement(4) is much poorer, possibly as
a result of neglect of work terms. Reactions of the trans-diaquo-N
4
-
macrocycles are slower than the corresponding hydroxy-aquo species in
contrast to expectations and these latter reagents may react by a hydroxy
bridge or by an inner-sphere mechanism.
Using rate constants derived from reaction of H2A and HA - with
[CO(OXh]3- and [Fe(phenh]3+, comparisons(5) of the Marcus-derived one-
electron potentials for H2A t IH2A and HA IHA - with molecular orbital
calculations for the HOMO energy confirm the greater reactivity of HA-
over H2A. It is pointed out(6) that the Marcus-derived potential for
HA/HA -,0.85-1.0 V, is greater than the best available measurement for
this parameter,(7) 0.68 V. The self-exchange rate for ascorbate radical is
10
2
_10
4
M-
1
S -1 and indicates a considerable barrier to electron transfer.
The ascorbate radical A" also has a high intrinsic barrier to electron transfer,
and detection(8) of second-order kinetics in the decomposition of A" sug-
gests a dimerization step with subsequent acid catalysis.
The effect of Cl- ion on the copper-catalyzed autoxidation of ascorbic
acid has been examined. (9) It is pointed out that the rate dependence on
[0
2
]1/2 can be explained by a mechanism involving a copper(I) intermediate
rather than the copper(III) proposed(10.11) earlier.
3.3. Quinols and Catechols
A study of the cerium(IV) oxidation of hydroquinone and hydroquin-
one esters has been undertaken(13) to investigate coupling of phosphoryla-
tion to two-electron oxidation. Reactions of substituted hydroquinones are
thought to be inner sphere since there is little rate variation with structure
(Table 3.2), and Marcus predictions lead to lower estimates of the rate.
Although slower than other hydroquinones, the phosphate and sulfate
esters show little difference in reactivity, implying that little P-O or S-O
stretching is required to obtain the semiquinone radical.
Hydroquinone has been used(14) to probe the reactivity of copper
complexes with substituted phenanthroline ligands where it is thought that
56 3

Metal-Ligand Redox Reactions
Table 3.2. Rate Constants and Activation Parameters for Reactions of Quinols
H
2
C and Catechols H
2
C at 25C
IL,
k,

as',
Reaction m
M-
1
S-1
kcal mol-
1
calK mol-l
Ref.
Ce(IV) + HOOPOj- 1.0 9.5 X 10
4
10.3 -15 13
Ce(IV) + HOOS0
3
5.9 x 10
4
8.9 -7
13
Ce(IV) + H
2
0 1.90 x 10
5
7.7 -9 13
Ce(IV) + H2O-CH3 1.04 X 10
5
13
Ce(IV) + H
2
O-SOH 1.42 x 10
5
13
Ce(IV) + H2O-OCH3 1.80 X 10
5
13
Ce(IV) + H
2
O-OH 2.87 x 10
5
13
Ce(IV) + H
2
O-Br 1.37 x 10
5
13
[Cu(dpmplz]2- + H
2
O
0.2 1.4 x 10
8
14
[Fe(phenh]3+ + H
2
O 1.0 1.02 X 10
8
4.5 -6.7 17
[Fe(phenh]3+ + H
2
C 1.0 9.2 X 10
6
5.5 -8.4 17
[Fe(phenhf+ + H
2
R
a
1.0 1.0 x 10
4
13.6 2.4 17
a Resorcinol.
reactions are outer sphere in nature. With the 4,7-bis(phenyl-sulfonated)
complex [Cu(dpmphf- where kinetic evidence for complex reorganization
has been reported, (15) no change in reaction order is detected, and the
copper(II) / (I) self -exchange rate is evaluated as 4.2 x 10
6
M-
1
S -1.
Rate constants in the cross-reactions between [Fe(phenhJ3+ and 1,2-,
1,3-, and l,4-benzenediols have been used to calculate(16,17) the reduction
potentials of the corresponding H2A t radicals. The values correlate with
HOMO energies derived from molecular orbital calculations. (8)
Considerable effort has been expended in studies of the interaction of
metal ions with catechols with a view to understanding oxygenase activity.
In aprotic media, the electrochemical properties of substituted catechols
have been examined. (19) Reactions of 3,5-di-tert- butyl-o -quinone with
manganese(II) result(20) in stable tris-Mn(IV) or bis-Mn(III) complexes of
the corresponding catecholate dianion, depending on whether the
initial ratio of reactants is 1: 3 or 1 :2. This flexible redox chemistry may
be important for redox catalysis. The O
2
oxidation of the iron-catechol
complex has also been examined(21,22) in aprotic
media.
3.4. Halogens and Pseudohalogens
The rate law for r reduction of copper(III) peptide complexes shown
in equation (2) is consistent with a mechanism depicted in equations (3)-(5),
3.4

Halogens and Pseudohalogens 57
rate = (2k
a
[r] + 2k
b
[I-]2)[Cu(III)] (2)
[Cu(III)(H-nL)] + 1-
Ko
[Cu(III)(H-nL)(r)] (3)
kl
[Cu(III)(H-nL)(rn
........
[Cu(II)(H-nL)] + r (4)

k_1
k2
[Cu(III)(H-nL)(r)] + 1-
........
[Cu(II)(H-nL)] + 1;- (5)

L2
where L represents a peptide ligand.(23) Linear free energy relationships
show that the first-order pathway with ka = Kokt, Table 3.3, is electron
transfer limited, while the second-order pathway, kb = Kok2' is rate limiting
in a step subsequent to electron transfer. A reduction potential for r of
;;;!: 1.2 V has been estimated.
Table 3.3. Rate Constants for Reactions of Metal Ion Complexes with Halides
and Pseudohalides at 25C
IL,
k,
Reaction M
M-1s-
1
Ref.
[Cu(H_
2
A
3
)] + r 1.0 4.5 23
kW] 1.28 x 10
3
M-
2
S-I
[Cu(H_
2
DGEN)] + r 1.0 4.5 23
kW]4.5 x 10
2
M-
2
s-
1
[Cu(H-
2
L
3
)] + 1- 1.0 2.6 23
kW] 5.5 x 10
2
M-
2
S-I
[CU(H-
3
G
4
a)] + 1- 1.0 0.23 23
kW]6.25M-
2
s-
1
[Cu(H_
2
Aib
3
)] + 1- 1.0
2 X 10-
2
23
kW]3.86M-
2
s-
1
[CU(H-
3
G
4
)f + r 1.0 0.10 23
kW] 1.4 M-
2
S-I
[Ni(H_
2
Aib
3
)] + r 1.0
k[Ni(III)]W] 3.0 x 10
10
M-
3
S-I
24
[Os(bipyhr + r a
k[r]3.33 X 10
4
M-
2
s-
1
25
[AuC1
4
r +1- 1.0 8.5 x 10
4
26
[AuBr4r +r 1.0 1.0 x 10' 26
[Co(py}zC0
3
(H
2
0ht + r 1.0
4.0 x 10-
2
27a
[Os(bipyh]2+ + 1;- a
1.1 X 10
8
25
[Os(bipyh]3+ + 1;- a 1.2 X 1010
25
[RhiOAc)4t + Br- 1.0
k[Br-] 8.1 X 10
2
M-
2
s-
1
27a
[Os(bipyhr + SCN- a
k[SCW] 25 M-
2
S-I
25
[AuBr4r + SCN- 1.0 5 X 10
4
27
[Au(SCN)4r + SCW 1.0 2.4 X 10
3
27
[Os(bipyhf+ + (SCN);- a 2.8 X 10
9
25
[Os(bipyhr + (SCN);- a 1.0 X 10
10
25
a 220C.
58 3 Metal-Ligand Redox Reactions
In the corresponding reduction(24) of [Ni(III)(H-
2
Aib
3
)r where Aib
is a -aminoisobutyric acid, the dependences on both [r] and [Ni(III)-
(H-
2
Aib
3
)-] concentrations are second order, indicating a concerted two-
electron exchange between [Ni(III)(H_
2
Aib
3
)(r)] complexes (1) to give
12 directly. A minor pathway involving two one-electron transfers with
participation of I; is also detected.
[Ni(11I) - I .. 1- Ni(III)]
1
The redox interactions of [Os(bipyhr+ and [Os(bipyhf+ with U and
formed by pulse radiolysis have been studied(25) and the reactions
are likely to be outer-sphere in nature since no intermediate adducts were
detected. This alfows calculation of the one-electron reduction potentials
for I;, hand (SCN); of 1.063, 0.172, and 1.331 V, respectively, at 22C
and 0.1 M ionic strength.
Reduction of [AuC1
4
r and [AuBr4r by 1- involves rapid attack by
outer-sphere r on coordinated halide (2) to give IX-, where X is CI or

2
Br. (26) Either a two-electron or a one-electron process with formation of
"Au(II)" is involved. In the presence of excess [AuX
4
r. rapid interhalogen
substitution reactions complicate the kinetic behavior.
Initial substitution [equation (6)] is involved in the corresponding
thiocyanate ion reduction. (27) This is followed by an electron transfer step,
[AuX4-" (SCN)"r + SCN- --. [AuX3-" (SCN),,+lr + X- (6)
first order in gold complex and [SCN-] in which reductive elimination
involving outer-sphere thiocyanate and coordinated halide or thiocyanate
is proposed. Cyanide, one of the eventual reaction products, inhibits the
reaction.
Two pathways are involved(27a) in the reduction of cis-
[Co(pyhC0
3
(H
2
0ht by r in aqueous media. Direct reduction by an
outer-sphere mechanism with rate constant 4.0 x 10-
2
M-
1
S -1 at 25C and
2.0 M ionic strength is in parallel with a pathway involving initial decar-
boxylation of the complex.
Oxidation of Br- by [Rh
2
(OAc)4t involves substitution to give
[Rh2(OAc)4Br] and [Rh2(OAc)4Br2r with stability constants 900 M-
1
and 150 M-
1
at 25C and 1.0 M ionic strength, respectively.(27b) Electron
3.5 Thiols, Sulfur, Selenium, and Tellurium Compounds 59
trander place through the bis complex with 11 rllte Constfint of 600 s-l
and though the structure of the complex involves a trans-Br- arrangement,
Br-Rh-Rh-Br, it is thought that the transition state for electron transfer
has the structure Rh-Rh-Br .. Br. Oxidation of [Rh
2
(OAc)4] by Ch at
120 M-
1
s -1 also involves two halogens in the transition state.
3.5. Thiols, Sulfur, Selenium, and Tellurium Compounds
The red complex(28) found in reaction of cysteine with [Fe(CN)sNO]2-
is a 1 : 1 complex as in equation (7) in which cysteine RSH is bound to the
[Fe(CN)sNOf- + RSH [Fe(CN)sNOSRf- (7)
NO ligand with a stability constant of 145 M-
1
at 25C and 1.5 M ionic
strength. The complex decays to [Fe(CN)sNO]3- and with a rate
constant of 1.8 x 10-
4
S -1 but is subject to equilibria involving loss or attack
by CN-. A purple vanadium(IV) complex has been detected as a product
in the vanadium(V) oxidation of cysteine. (Z9) It is thought to be a bis-cysteine
adduct. Acid decomposition of [(enhCo(SCH
z
CH
2
NH
z
)]2+ is first order in
the complex, independent of [H+], with a rate constant of 2.10 x 10-
6
S-l
at 56C and 1.0 M ionic strength.(30) The products are Co
z
+, and
a thiyl radical which dimerizes to form cystamine.
Oxidation of 2-thiouracil by [Fe(phenh]3+ is first order in each reagent
and proceeds(31) at a rate of 4.14M-
1
S-l at 25C and pH 2.3. However,
[IrCI
6
]2- oxidation of methylated-2-thiopyrimidines, RSH, shows two path-
ways respectively, first and second order in substrate. For the [RSHf
pathway, a mechanism involving equations (8)-(9) is proposed. All the
reactions show pH dependencies ascribable to pKa values of the thiols.
[IrCI
6
f- + 2RSH ---+ [IrCI
6
]3- + + 2H+ (8)
[IrCI
6
f- + (RS)2" ---+ [IrC1
6
]3- + (RSh (9)
Under anaerobic conditions,<3Z) the copper(III)-tetraglycine complex,
[CU(H-
3
G
4
)]-, oxidizes to S03 in two one-electron steps (10) and
(11). The S03 formed subsequently hydrolyzes to sulfate with a rate
k,
[CU(H-
3
G
4
)r + [CU(H_
3
G
4
)]z- + S03 (10)
L,
(11)
constant k
3
. Values for k1 = 3.7 X 10
4
M-
1
s-t, kz/L1 = 1.66 and
k-z/k3 = 1.77 M-
1
are calculated at 25C and 0.10M ionic strength and
lead to an upper limit of 0.89 V for the SO:3 reduction potential. In the
presence of oxygen, S03 reacts with O
2
to produce a strongly oxidizing
SOs species.
The oxygen-bound sulfate complex [Co(tren)(OH
2
)OS02t is
formed(33) by reaction of [Co(tren)(OH
2
)OH]2+ with and undergoes
internal electron transfer to give cobalt(II) and SO i- with a rate constant
1.0 X 10-
3
S-l at 25C and pH less than 5.4. Activation parameters are
MI* 24 kcal mol-
l
and as* 8.2 cal K-
1
mol-I. At higher pH a bis-sulfite
complex which is not subject to internal redox is formed. Infrared evidence
points to both Sand 0 binding in this species.
Two papers dealing with the trans-[Os(OHh04] oxidation of thiosul-
fate have appeared. The mechanism(34) involves intermediate complex
formation shown in equation (12) with a formation constant of 6.12 at
[Os04(OHhf- + [Os04(OH)S203]3- + OH- (12)
30C and 0.32 M ionic strength followed by electron transfer to give
[Os04(OH)H20f- and the S203 radical which subsequently dimerizes. In
the presence(35) of [Fe(CN)6]3-, the intermediate undergoes an outer-sphere
reaction to give [Os04(OHh]2- and the S203 radical.
With excess thiourea, (36) OS04 undergoes reduction to give an
[Os(thiourea)6]3+ product. The rate, in aqueous ethanol, is acid catalyzed
and two pathways (k
l
+ k
2
[H+]) involving thiourea are indicated. Values
for kl and k2 are 0.35 M-1s-
1
and 0.34M-
2
s-
1
at 20C. In 75% acetic
acid solution(37) HCrO; oxidizes diphenyl sulfoxides, Ph
2
SO to Ph
2
S0
2
.
The reaction is first order in each reagent and is accelerated by electron-
releasing substituents on the phenyl groups.
The rate law(38) for Ce(IV) oxidation of Se(IV) in 4 M HCI0
4
at 50C
is given by equation (13). The proposed mechanism involves formation of
a complex [equation (14)] followed by reversible electron transfer [equation
(15)] and subsequent Ce(IV) oxidation to Se(VI) [equation (16)]. Rate
constants are K = 127 M-
1
, kl == 3.3 X 10-
4
S-l and k3/k2 = 2.0.
2k
1
k
2
K[Ce(IV)f[Se(IV)]
rate = k
2
[Ce(III)] + k
3
[Ce(IV)](1 + K[Se(IV)]) (13)
K
Ce(IV) + Se(IV) [Ce(IV)Se(IV)]
k,
[Ce(IV)Se(IV)] Ce(III) + Se(V)
k,
Ce(IV) + Se(V) Ce(III) + Se(VI)
(14)
(15)
(16)
Complexation is also involved(39) in the corresponding reaction with
Te(IV) although the rate law is more complex and Te(VI) accelerates the
redox process.
3.6 Amines
61
3.6. Amines
The mechanism of oxidation of [(bipy)zRu(2-CH2NH2py)]2+ by Ce(IV)
has been investigated(40) in 1.0 M H
2
S0
4
. The eventual product is
[(bipy)zRu(2-CH = NHpy)]2+ where net two-electron oxidation of the
coordinated aminopyridine has taken place. Limited one-electron oxidation
gives the ruthenium(III) complex [(bipy)Ru(2-CH
2
NH
2
Py)]3+ with a rate
constant of 5 x 10
5
M-
1
s -\ comparable to oxidation of [Ru(terpy)-
(bipy)NH
3
f+ with a rate constant of 6.1 x 10
5
M-
1
S-1 where no ligand
oxidation can take place. Deprotonation of the ruthenium(III)-amine com-
plex with pKa 2.4 and ensuing comproportionation of [(bipy)zRu(2-
CH
2
NH
2
Py)]3+ and [(bipy)zRu(2-CH
2
NHpy)]2+ with a rate constant of
6 x 10
8
M-
1
S -1 gives one equivalent of the desired product and one of
[Ru(2-CH
2
NHpy)]3+, a formal ruthenium(IV) species which decays at a
rate of 102 s -1 to give a second equivalent of the product.
An intermediate absorbing around.480 nm is detected(41) in the oxida-
tion of triphenylamine by Ce(IV) and Fe (III) in ace to nitrite solution. This
is not an amine cation radical as previously claimed and it decomposes to
give tetraphenylbenzidine dication.
The 2: 1 oxidation of hydrazine, N
2
H;, by the chromium(V) chelate
[CrO(OCEt
2
C0
2
)zr involves(42) initial dissociation of a (OCEt2C02)2-
ligand followed by a two-electron inner-sphere redox process giving
[Cr(OCEt
2
C0
2
)t and N
2
H
2
, which subsequently reacts in a further two-
electron step with [CrO(OCEt
2
C0
2
)t to give N
2
.
Ferricyanide oxidation(43) of phenylhydrazine is complicated by pro-
tonation of the reductant with pKa values 5.36 and -1.69. Rate constants
for the species increasing in protonation are 9.46 X 10
2
M-
1
s-\ 8.3 x
10-
2
M-
1
s-t, and 7.9 M-
1
S-1 all at 25C and 1.0 M ionic strength. Elec-
tron-releasing substituents accelerate(44) the rate oxidation of phenylhy-
drazones by thallium(III) in 90% acetic acid.
In carbonate solution, inhibition from in the Ce(IV) oxidation
of semicarbazones(45) suggests participation of a [Ce(IV)-semicarbazone]
intermediate complex. With acetone-semicarbazone, this complex has a
stability constant of 13.4 M-
1
and decays with a specific rate of 23.8 x
10-
4
s -1 to give a nitrogen-centered radical.
The hydrolyzed oxidant AgOH+ is the active species in reaction(46)
with N -methyl formamide derivatives in strong HCI04 media. Initial reac-
tion involves C-N bond scission [equation (17)] with formation of a metal-
bound C-centered radical which is further oxidized to give CO
2
.
AgOH+ + HC(O)NHCH
3
-+ HCO(HO)Ag + + NHCH
3
(17)
A manganese(IV) species absorbing around 300 nm is formed in the
permanganate oxidation of substituted uracil derivatives. (47) The rate-
determining step is addition of MnO; over the C(5)-C(6) bond with a rate
constant of 1.94 M-
1
s -1 in the case of uracil itself.
Riboflavin, Rb, can be reduced(48) in two one-electron steps with
potentials of 0.22 and 0.15 Y in 1.0 M acid at 25C to RBH' and RBH
2
,
dihydroriboflavin. Both processes can be detected in reduction by y2+ with
rate constants of 8.0 x 10
4
M-
1
S-1 and 3.6 x 10
4
M-
1
S-1 at 21C and
0.12 M HCI0
4
which are too fast to be inner sphere in nature. No sub-
stituent effects have been detected in the oxidations of RBH' by a variety
of metal ion oxidants including a series of substituted cobalt(III)-
pentaamine derivatives, and these reactions are also considered to be outer
sphere in nature. Similar results are reported for dihydroriboflavin, (49) and
the presence of an unreactive protonated radical RbHi with a pKa 0.89
has been detected.
Electron transfer catalysis of the reaction between Eu
2
+ and
[(NH
3
)sCopy]3+ using substituted derivatives of 2,4-pyridine dicarboxylic
acid involves(SO) initial reversible Eu
2
+ reduction of the catalyst followed
by oxidation by the cobalt(III) complex. Catalyst deterioration takes place
by dimerization (> 10
8
M-
1
s -1) and further Eu
2
+ reduction (0.7-4.0 x
10
2
M-
1
S -1) and can be slowed substantially by using the N -methylated
derivatives. So-called "interrupted catalysts" where the carboxylate group
is not in conjugation with the pyridine ring enhance(Sl) the reaction rates
by more rapid Eu
2
+ reduction.
A very stable radical [Co(NH
3
h(NNNOH)]2+ is formed(52) on addition
of 'OH to azidopentaammine cobalt(III). At 25C, this undergoes
intramolecular electron transfer with a rate constant of 60 s -1 to yield
cobalt(II), N
2
, and N
2
0.
3.7. Carbonyls and Carboxylic Acids
Isotope effects have been used to examine(S3) the HCrO; cooxidation
of 2-hydroxy-2-methylbutyric acid and propan-2-01. The reaction involves
the proposed intermediate 3, which decomposes to give EtCOMe, Me2CO,
Me

- Cr=O
C __ o/I
rf' 0 Hili

Me Me
3
3.7 Carbonyls and Carboxylic Acids
63
and 'C0
2
H radical. As acidity in the reaction medium is increased, kH/ ko
for labeled H* increases while ke
12
/ k
e
13 for C* decreases, signifying a
change in the rate-determining step from formation to decomposition of
the ternary complex. Two steps are involved in the decomposition: a
two-electron oxidation of the alcohol involving C-N cleavage and a one-
electron process giving C-C scission in the carboxylic acid giving an overall
three-electron oxidation.
Oxidation of aliphatic acids by Ag2+ shows(54) a slight dependence on
[Ag +] but the rate-determining step is electron transfer to Ag2+ or AgOH+.
The rate constants increase from 5.59 M-
1
S-1 to 8.55 X 10
3
M-
1
S-1 for
Ag2+ and 4.68 x 10 M-
1
S-1 to 2.79 X 10
4
M-
1
S-1 for AgOH+ on changing
the structure of the acid from acetic to the more electron-rich pivalic. Acid
inhibition is explained on the basis of unreactive species. Osmate
catalyzes the [Fe(CN)6]3- oxidation of 2-bromo-propionic acid by a
mechanism in which decomposition of a 2-bromopropionate complex with
[Os04(OHhf- is the rate-determining step.(55)
Reactions of cerium(IV) with mandelic acids in perchlorate media
reveal the presence of intermediate complexes with p-Cl-mandelic acid,
HL. Two intermediates, [CeHLt+ and [CeL]3+, are observed,(56) but only
[CeL]3+ is reactive with a rate constant of 45 s -1 at 20C and 1.5 M ionic
strength to give cerium(III) and a mandelate radical, which subsequently
reacts to give CO
2
and p-Cl-benzaldehyde. Similar results are found with
the p -N0
2
-substrate(57) but with p -methoxy-mandelic acid, additional [H+]
catalysis points to the operation of a different mechanism. Other decarboxy-
lation mechanisms with Ce(IV) have been examined. (58) With ethyl-
acetonacetate, CH3 COCH
2
C0
2
Et, in 0.5 M nitric acid, CeOH3+ reacts
directly(59) with the substrate to give a radical which undergoes C-C scission
to give CO2, HC02H, and two moles of acetic acid. Activation parameters,
in particular a positive (28 cal K-
1
mol-I), implies that there is no
complex formation in the transition state.
Decarboxylation(60) of a -amino-a -isopropyl malonate, chelated to a
cobalt(III) N
4
-chelate, where N4 is a chiral tetradentate amine ligand, in
acidic media gives valine with considerable asymmetric induction. With
N4 = 1,7-bis(2(S)-pyrrolidyl)-2,6-diazaheptane, the ratio of S:R isomers
is 2 : 98 and it is thought that attack by H+ is obstructed in this case by the
in-plane pyrridoline ring and the bulky isopropyl substituent on the malon-
ate. Other substituents show lesser asymmetric induction. The reaction
kinetics are pH dependent with a pKa - O.
The rates of oxidative decarboxylation of amino acids by the cop-
per (III) complex [Cu(I0
6
hf- increase with increasing pKb of the sub-
strate.(61) Periodate inhibition in the rate law suggests formation of a
complex between the amino acid and [Cu(I0
6
)]2-, which decomposes in
64
3 Metal-Ligand Redox Reactions
the rate-determining step. Bromide ion catalysis(62) in the oxidation of
glycine by MnO; involves two pathways. Rate-determining Br2 formation
by permanganate oxidation of Br - followed by rapid attack on the substrate
gives a rate term independent of [glycine]. However, a term-dependent on
both [Br -] and [glycine] can best be explained by involvement of a Br --
glycine ion pair for which spectrophotometric evidence is presented. Initial
results of a reinvestigation(63) of Mn(II) catalysis in the MnO; oxidation
of oxalate have also been reported.
Decarboxylation of pyruvate ion, CH
3
COC0
2
, by [Fe(CN)6]3- is
catalyzed(64) by OH- and involves oxidation of the dianion
CH
3
CO-(OH)C0
2
by [Fe(CN)6]3- in the rate-determining step to give an
oxygen-centered radical. Alternative decomposition pathways involve rear-
rangement to oxalate and a CH
3
radical or direct [Fe(CN)6]3- attack to
give CO
2
and acetate ion. With Eu
2
+, the reaction is acid catalyzed(65) and
involves initial attack of Eu
2
+ on the ketoacid to give a carbon-centered
radical followed by further reduction to give lactic acid as the product.
The effects of H
2
0-dioxane mixtures have been examined on the
Mg2+, Mn2+, and Zn
2
+ -catalyzed decarboxylation of oxaloacetate. (66) The
mechanism involves metal-oxaloacetate complex formation and though
the rates are considerably enhanced, complications from the formation of
enolate complexes are detected. The results of these studies are com-
pared(67) with metal ion catalysis in the presence of pyruvatekinase and it
is concluded that bonding is aided by the presence of the metal ion but
that other enzyme functional groups promote decarboxylation.
Manganese(III) oxidation of cyclohexane in perchloric acid media(68)
to give (CH
2
MC0
2
Hh is independent of [Mn2+] and the rates are faster
than the rate of cyclohexane enolization in contrast to the behavior in
acetic acid media. The mechanism is thought to involve outer-sphere
oxidation of the keto form by Mn3+ and MnOH
2
+ with rate constants of
3.08 x 10-
3
M-
1
S-1 and 1.58 x 10-
2
M-
1
s-1 at 4M ionic strength and
25C. The initial radical product is further oxidized. No spectrophotometric
evidence is found for an intermediate complex though a hydroxyl-bridged
mechanism cannot be ruled out. Activation parameters for the two pathways
are /).j{* 27 kcal mol-t, tJ..S* 20 cal K-
1
mol-t, and /).j{* 25.4 kcal mol-t,
tJ..S* 17 cal K-
1
mol-t, respectively.
3.8. Alcohols and Diols
The rate law for oxidation of alkane diols by cerium(IV) in nitric acid
media suggests formation of intermediate Ce(IV)-diol complexes. (69) With
substrates where the -OH groups are separated by five or more carbon
3.9 Alkenes and Alkyls 65
atoms, a monomeric Ce(IV) species is involved, whereas if the separation
is four or less carbon atoms, a dimeric oxidant is reactive. The silver(II)
ion AgOH+ reacts(70) with ethylene glycol at a rate of 1.3 x 10
6
M-
1
S-l
to form a complex [AgOH(CH
2
0Hht, which subsequently decays to Ag+
and the alkoxyl radical'OCH
2
CH
2
0H with a rate of 2.8 x 10
3
S-l at 22C.
The radical undergoes (3 scission to give CH
2
0 and CH
2
0H. The latter
reacting with Ag + to give a second mole of CH
2
0.
The silver(III) complex [Ag(OH)(H)(I0
6
h]'- oxidizes primary and
secondary alcohols(71) to the corresponding carbonyls with 1 : 1
stoichiometry and the rate law (18) suggests a complexation mechanism.
No evidence is found for radical formation.
(18)
A similar rate law is observed(72) in reaction of cyclic secondary alcohols
by [Cu(OHhH4Te06r. where the rate is independent of ring size C
S
-C7
This points to rate-determining O-H rather than C-H bond scission in the
proposed [CuOH
2
TeOsROHr complex. The reaction is catalyzed by
OS04.
Limiting kinetic behavior in the [IrCI
6
]2- oxidation of alcohols,
R
1
R
2
CHOH (R
h
R2 = H, Me) points to formation(73) of an intermediate
complex which decomposes with C-H cleavage to give a carbon-centered
radical in the rate-determining step. The absorbance at 488 nm increases
and lack of Cl- inhibition points to a seven-coordinate geometry for the
intermediate.
In benzene solution(74) with 1% acetic acid, oxidation of benzyl
alcohols, ROH, to benzaldehydes by Pb(OAc)4 is second order in substrate,
consistent with formation of an intermediate bis complex Pb(OAch(ORh.
No radicals are detected and a two-electron transfer oxidation of one of
the coordinated alcohols is proposed. In the presence of pyridine, the
reaction is first order in both alcohol and pyridine and a large isotope effect
suggests proton abstraction by pyridine in the rate-determining step.
3.9. Alkenes and Alkyls
Four-electron oxidation of alkenes to a -ketols proceeds through
similar cyclic hypomanganate esters to those found in the two-electron
glycol formation.(7S) Labeling experiments indicate, however, that a cyclic
manganese(VI) ester undergoes oxidative decomposition to an acyclic
manganese(IV) derivative which yields the product on hydrolysis. Labeling
66
experiments(76) are also consistent with a five-coordinate manganese inter-
mediate in the oxidation of 1,5-hexadiene.
Pulse radiolysis studies(77) of the reactions between a -substituted alkyl
radicals and [IrCI
6
f- indicate two distinct processes. Diffusion-controlled
rates with a -OH and a -OR derivatives involve electron transfer, while,
with alkyl and alkylchloride radicals, a chlorine atom transfer from [IrCI
6
]2-
to give [IrCI4(OHhf- predominates with considerably slower rate con-
stants. The comparable reactions with [Fe(CN)6]3- are also slow and struc-
ture dependent but there is no evidence for CN transfer.
In acetonitrile solution, (78) two processes are also noted in the rapid
reactions of alkyl radicals with [M(bipyh]3+, where M is Fe, Ru, or Os.
An outer-sphere oxidation of the radical forming a cation is in agreement
with Marcus correlations. The cation can rearrange and subsequently
decompose to form an alkene or react with solvent to give an alkyl
acetamide. In the other pathway, there is considerable steric inhibition and
an inner-sphere mechanism in which the radical substitutes on the
phenanthroline ring is proposed.
Reduction of 1.1. -superoxo-cobalt(III) dime ric complexes by
isopropanol radical(79) is faster than with other a -hydroxyradicals where
reaction is at the 1.1. -0
2
bridge giving a 1.1. bridge. It is thought that in
the isopropanol case, reduction takes place at a metal center giving an
end-bonded 1.1. -0
2
bridge.
The complex [(H
2
0hCrCH
2
CH
2
0H]2+ decomposes(80) in acidic media
to give [Cr(H
2
0)6]3+ and ethylene by a mechanism dominated by an acid
catalyzed pathway with a second-order rate constant of 1.43 x 10
4
M
1
- S-1
at 24.1 C and 0.05 M ionic strength. Normal acidolysis would yield ethanol
as a product and it is proposed that water is first eliminated giving a bound
ethylene molecule.
Compounds of the type CrR2+ exist in equilibrium(81) with Cr
2
+ and
R' and are a convenient source of organic radicals.
7
Coupling reactions of
organic radicals with the benzyl substituents in [PhCH
2
Co(dmgHh(H
2
0)]
have been examined using competition reactions of R' with [Co(enh]3+ in
1.0 M acid solution at 25C, rates are 1.7 x 10
7
M-
1
S-1 and 1.2 x
10
7
M-
1
S-1 for reactions of 'CHCH
3
0Et and 'C(CH
3
hOH radicals.
3.10. Nitrogen and Nitrogen Oxides
Mechanistic investigations of the reaction of trans-
[Mo(NH)X(dppeht, where X is a halogen and dppe is Ph2PCH2CH2PPh2,
in basic methanol to give ammonia have been reported. (82) Initial deproto-
nation of the substrate by methoxide or added ElJN is followed by rapid
3.10 Nitrogen and Nitrogen Oxides 67
dissociation of the halide k > 300s -1 to give an ion pair except in the case
of fluoride ion, where dissociation is rate limiting with a rate of 1.78 S-l.
Methoxide attack on the ion pair takes place with a rate constant of
1. 7 x 10
6
M-
1
S -1 to give, after proton abstraction from solvent,
[Mo(OMe)(NH)(dppeht. Further reaction is rate limited by phosphine
ring opening with a rate of 1.57 x 10-
4
s -1 to yield a product which contains
coordinated NH
3
.
Studies using nmr(83) reveal the presence of hydrazid0
2
- complexes in
the reaction of cis-[M(Nh(PMe
2
Ph)4], where M is Mo, or W, with H
2
S0
4
in thf solution and the species [M(NNH2)(HS04h(PMe2Phh] can be
isolated. Similar complexes react with H
2
S0
4
or BH; to give NH3 and
N2H4 in methanol solution. The corresponding reactions of trans-
[M(N
2
h(dppeh] with HX, where X- is Cl-, Br-, or HSO; in thf solution,
have been investigated. (84) Initial HX adduct formation is followed by
protonation of one of the nitrogen ligands with further moles of HX and
is in turn followed by rate-limiting dissociation of the trans N2 ligand to
give the product trans-[M(NNH
2
)X(dppeht. Side reactions with HCl in
which the HX adduct rearranges to give hydrido complexes are also
detected.
A monomeric varadium(II)-pyrocatedol complex, Y(II)PC, is in-
volved(85) in reduction of N2 and a variety of acetylenes. Hydrogen is
evolved in the presence of no reducible substrate and the mechanism
involves a two-electron transfer to give Y(IY)PC. Reduction of N2 gives
initially diimide N2H2 as a product, which then disproportionates to yield,
eventually, NH3 and hydrazine. Nitroamine, NH
2
N0
2
, is reduced by y2+
and Cr
2
+ in acidic media.(86) With vanadium(II), the reaction has
stoichiometry 1 : 2 yielding N2 as the sole product [equation (19)]. Labeling
2y
2
+ + 2H+ + NH
2
N0
2
-. I'h + 2H
2
0 + 2y
3
+ (19)
studies indicate no N-N bond cleavage in the reaction which probably
involves NH
2
NO as an intermediate. With chromium(II) however, further
reduction to give 75% NH3 and only 25% N2 is involved. Hydrazine cannot
be involved and a chromium(III)-bound hydrazide
2
- species, Cr(III)NNH
2
,
is proposed as a possible intermediate.
The formation of FeN0
2
+ is enhanced(87) by the presence of acetate,
probably coordinated as the monoacetate complex. At pH > 4, a bis-
nitrosyl complex forms with a formation constant of 15 atm -1 at 25C,
pH 6.0, and 3.0 M ionic strength and this decays by a minor first- and a
major second-order pathway giving N
2
0.(88) Rate constants are 1.6 x
10-
4
S-l and 0.047 M-
1
s-t, respectively. Tracer studies rule out solvent
incorporation in the product and it is suggested that an NON bridged
intermediate is involved.
At 111C in tolulene solution(g9) the complex [Ru(N0
2
h(COh(PPh
3
h]
decomposes in the presence of excess PPh
3
to give [Ru(NOh(PPh
3
h], CO
2
,
CO, and Ph3PO. Two selective 0 transfers are involved and labeling studies
show that statistical scrambling takes place intramolecularly between the
oxygen on CO and N0
2
before CO
2
loss which is the initial process giving
[Ru(N0
2
)(CO)(NO)PPh
3
h] as an intermediate. However, the mechanism
of 0 transfer is consistent with an intermolecular process.
Reductions of HN0
2
and NO
z
by [Fe(Me4phenhf+ have rate con-
stants of 7.26 x 10
2
M-
1
S-1 and 2.57 x 10
4
M-
1
S-1 at 25C and 0.5 M
ionic strength. (90) The reactions are outer sphere and reflect electrostatic
interactions. Protonation of the initial product HNO
z
gives NO on
decomposition.
Vanadium(V) oxidizes HN0
2
to give NO)" in a reaction(91) with a rate
law shown in equation (20). Acid catalysis suggests reversible reduction
2k
1
k
3
K[VO;]2[HN0
2
][H+]
rate = + (20)
k
2
[N0
3
] + k
3
[V0
2
]
of by HN0
2
to give NO)" and vanadium(III) as an initial step.
The third-order rate constant for the forward reaction is 8.51 M-
2
S-1 at
30C and 1.0 M ionic strength. Subsequent reaction between V(III) and
YO; completes the process.
The oxidation of H
3
P0
2
by Ag2+ proceeds(92) at a rate of 7.6 x
10
2
M-
1
S-1 at 30C and 4.0M HCI0
4
. There is no evidence for involve-
ment of Ag(III) or intermediate complexes but inhibition by Ag + is ascribed
to strong complexation of this reagent with the substrate. This strong
complex, AgH
3
PO;, is not an active species in the corresponding reduc-
tion(93) by Ag+ which proceeds with a rate constant of 5.2 x 10-
2
M-
1
s-1
at 30C.
3.11. Peroxydisulfate and Peroxymonosulfate
The iron(III)-catalyzed oxidation of hydrazine with involves(94)
formation of mixed hydrazine-peroxydisulfate iron (III) complexes
[equations (21)-(23)], with values for the rate constants k1 and k2 of
Fe3+ + [FeS20gt (21)
[FeS20gt + N2Hs + H+ + [FeS20g(N2H4ht (22)
[FeS20gN2H4t + H+ + [FeS20g(N2H4ht (23)
2 x 10-
3
S-1 and 4.9 x 10-
3
s-t, respectively, at 45C and 0.1 M ionic
strength. The protonated complex [FeS20g(N
2
H
4
)(N
2
H
s
)f+ was also
3.11 Peroxydisulfate and Peroxymonosulfate 69
detected but is unreactive. Iron(II) produced in the reaction is rapidly
oxidized by peroxidisulfate and the rate law for this reaction [equation
(24)] has also been examined.(95) The proposed mechanism involves reac-
(24)
tions of and with rate constants kl = and
Kk2 = 55 s at 30C and 1.0 M ionic strength where K is the proton-
ation constant of the oxidant. Reaction of the complex
has a rate constant of 0.19 at 25C and 0.033 M ionic strength.(96)
Protonated species HS
2
0i! and H
2
S
2
0
8
are also involved(97) in the
acid decomposition of peroxydisulfate which is strongly catalyzed by Ag +.
It is thought that the [Ag +]-dependent pathway involves formation of a
AgS
2
0i! complex. Silver(I)-catalyzed oxidations of organic sub-
strates in general involve initial, rate-determining Ag(II) formation
[equations (25) and (26)]. In reactions with alicyclic alcohols, radical species
+ Ag(I) --. Ag(II) + + SO';- (25)
SO';- + Ag(I) --. Ag(II) + (26)
are involved in the mechanism, (98) whereas with dmso, no radicals are
detected and rapid oxidation of (CH
3
hS+ =0 by to give
(CH
3
hS
2
+ =0 is proposed.(99)
An alternative mechanism has been suggested(lOO) for the copper-
catalyzed oxidation of malic acid. The originally proposed(lOl)
decomposition of a copper(III)-malate intermediate complex
[Cu(C4H40 5hr to give CuC4HsO and two radical fragments CO
2
and
is without precedent and a single radical
'02CCHOHCH
2
C0
2
is more likely.
Cocatalysis of the decomposition of peroxomonosulfate HSO
s
by Ag +
and involves(102) reaction (27) in the rate-determining step. The
(27)
silver(II) formed oxidizes HSO:5 to HSO and O
2
, a product in the reaction
is produced from the terminal peroxyl oxygen by a dimerization mechanism.
(28)
Oxidation(103) of V02+ by HSO:5 has a simple rate law [equation (28)]
with k = 12.8 s and MIt = 12 kcal and =
-11 cal and the mechanism was shown to involve radicals
using cerium(III) and azide as radical traps. The clean behavior of HSO:5
on one-electron reduction is contrasted with corresponding reductions of
H
2
0
2
and is ascribed to the low occurrence of HSO
s
. Rate law (28) was
also found(1041 operative in the oxidation of YO;. The SO; radical formed
by reduction of HSOs oxidizes VO; to which cleanly decomposes
to give V0
2
+ and O
2
Competitive rates of reaction of SO; with VO; and
V0
2
+ are in the ratio 38: 1. Similar behavior is noted in the oxidation of
VO; by Co3+ and the clean reactivity of the one-electron oxidized product
is considered of value in distinguishing between one- and two-
electron processes.
Oxidations (105) of a number of metal ion species by fluoroxysulfate,
S04F- involve reaction (29) in the rate-determining step with a second-
order rate constant of 1.3 x 10
3
M-
1
S -1 at 17C and t:Jl* 6.1 kcal mol-
1
and !::.s* -23 cal K-
1
mol-I. In the absence of Ag+, the reactions are slow
and complex.
(29)
Although not a reaction of a peroxy compound, the Ag + -catalyzed
oxidation of H
2
0 by Ce(IV) is included because it involves production of
Ag(lI), the active H
2
0 oxidant, by reaction with CeOH
3
+ with a second-
order rate constant of 4.0 x 10-
3
M-
1
S-1 at 30c.(106)
3.12. Oxyhalogen Anions
The rate law(107) for 104"(H
4
106") oxidation of chromium(III) to
chromium(VI) has a second-order dependence on [Cr(III)] concentration
and the reaction involves formation of a periodate-bridged chromium dimer
[Cr(OH)10
4
HCrOHt+ which decays at a rate in excess of 1.29 x 105 S-1
at 25C and 0.25 M ionic strength with two simultaneous one-electron
transfers from the metal centers to the bridge.
Oxidation(108) of cobalt(II) aminocarboxylates [CoHEDTAr and
[CoEDDA] by 104" is first order in metal complex but two pathways with
first- and second-order dependencies on [104"] concentration are detected,
indicating intermediate mono- and bis-complex formation. Both complexes
are redox active and second- and third-order rate constants are
0.16M-
1
s-
1
and 2.59M-
2
s-
1
for [CoHEDTAr and 0.120M-
1
s-
1
and
1.53 M-
2
s -1 for [CoEDDA] at pH 5, 25C, and 0.5 M ionic strength. The
third-order rates are pH dependent.
Three different reactions are detected(109) in the 10
4
oxidation qf
2,3-dihydroxypropyl cobalamin. Period ate attacks the diol function of the
"base on" and "base off" complexes with acid-catalyzed rate constants of
2.4 x 10
6
M-
2
S-1 and 2.0 x 105 M-
2
S-1 to give B
12a
in a pathway which
71
involves a period ate diester intermediate. In the presence of excess
cobalamin, this intermediate reacts to give formyl methyl cobalamin and
eventually the B 1Za product. Period ate attack on B 1Za occurs only at high pH.
The period ate oxidation of [W(CN)st- is first order in both
reagents(llO) and exhibits an acid dependence which can be explained by
pathways (30) and (31) with rate constants 1.66 x 10
5
M-
1
S-1 and
W(CN); + H
4
10;S -. products
W(CN); + -. products
(30)
(31)
1.58M-
1
s-\ respectively, at 30C and O.lM ionic strength. Osmate
catalysis(111) in the 10; oxidation of unsaturated organic acids involves
formation or decomposition of complex intermediates in the rate-limiting
step depending on the substrate structure.
Reaction of 103" with H3As03 has been investigated(11Z) using a stirred-
flow system and its relation to the 103" /H
3
As0
3
/ClO
z
oscillating system(113)
explored. A number of other studies on oscillating reactions involving
oxyhalogen anions have been reportedY
14
)-(1Z0)
In 0.1 M perchloric acid, RuCh catalyzes(121) the oxidation of primary
and secondary alcohols by Br03". The rate-determining step does not
+
involve Br03", but hydride abstraction by ruthenium(III) to give RCHOH
intermediates takes place. The role of Br03" is in reoxidation of the
ruthenium-hydride produced in a two-electron step to give Br(III).
Chlorate oxidation of [Fe(CN)6t- follows(1ZZ) a rate law [equation
(32)] where a is dependent on acid, buffer, and the cell material, while b
a [CIOz][Fe(CN):-]
rate = b + ]
(32)
is acid dependent. The proposed mechanism involves a reversible one-
electron transfer (33) which can be catalyzed on the cell walls followed by
further reaction of
[Fe(CN)6t- + -. [Fe(CN)6]3- + (33)
3.13. Reactions of O
2
and H
2
0
2
Reaction of O
2
with the complex [(H
z
O)sCrCH(CH
3
hf+ to give
[Cr(H
Z
O)6]3+ and acetone proceeds by a chain mechanism(123) initiated by
chromium-carbon bond cleavage with a rate of 1.74 x 1O-
4
s-
1
at 25C
and 1.0 M ionic strength. Inhibition studies suggest the organic radicals
(CH3hCH and (CH
3
hCHO; are chain intermediates involved in the reaction
72
(34). Alternative chain carriers Cr
2
+ and can be excluded on the
basis of ionic strength effects.
(CH
3
hCHO; + Cr-CH(CH
3
h -. (CH
3
hCH0
2
Cr + CH(CH
3
h (34)
Autoxidation of a,p, y,5 -tetraphenylporphorin-chromium(II),
[TPPCr(II)], in tolulene solution proceeds in two stages(124) with intermedi-
ate formation of a /L -oxo-chromium(lII) complex [TPPCr(III)]20 prior to
the chromium(lI) product [TPPCr(IV)O]. Reaction of [TPPCrO] with
[TPPCr(II)] yields the chromium(lII) dimer. A pH-dependent equilibrium
involving intramolecular electron transfer between Mn(II)-02 and Mn(III)-
0;- is observed(125) in the reaction of a tetrasulfonated-phthalocyanine
manganese(II) complex with O
2
. The superoxide species is found only at
pH 11.5-13.5. A manganese(II)-02 complex is also required to explain(126)
the absence of spectroscopic characteristics for both (II) and (III) oxidation
states of manganese in the reaction of a trivalent pentadentate Schiff base
derivative with O
2
.
Electrochemical reduction
(27
) of trans-[Co([14]aneN
4
)(OH
2
h]3+ in
0.5 M HCI04 leads to formation of the corresponding cobalt(II) species
which, with O
2
in stoichiometric deficiency, reacts giving a /L -peroxo
complex. However, with O
2
in excess, the reaction product can be reduced
to give a trans-[Co([14]aneN
4
)(OH
2
)(02H)f+ end-bonded hydroper-
oxide complex which subsequently decomposes to give cobalt(lI) and H
2
0
2
.
Initial reaction with O
2
is too fast to measure electrochemically but is
consistent with previous studies on this reaction. (28)
Redox decomposition(2
9
) of the /L -peroxo complex
[(enhNH
3
Co/L 02CoNH3(enht+ is independent of [H+] with a first-order
rate constant of 4.9 x 10-
3
S-1 at 25C and 0.1 M ionic strength and
activation parameters 132 kJ mol-
1
and 151 J K-
1
mol-
1

Ruthenium complexes [Ru(EDTA)r and [Ru(HEDTA)] react slowly with
O
2
to give /L 02/L OH complexes which are best considered as
ruthenium(IV), [(EDTA)Ru(IV)/L O
2
, /L OH Ru(IV)(EDTA)]3- in which
the metal ion is 7 coordinate. (130)
In benzene solution the rate law for oxidation 2,6-dimethyl-phenol
by O
2
catalyzed by the bis(3-(salicylideneamino)propyl) methylamine com-
plex of cobalt(II), [Co(SMDPT)], is (35), which suggests(131) participation
of a Co-0
2
complex in which the oxygen is activated to H abstraction.
rate = k[Co(SMDPT)][2,6-Me2phenol][02] (35)
The rate of oxidation(132) of 2,6-ditertiarybutyl,-4-substituted phenols
by O
2
, catalyzed by cobalt(II)-Schiff base complexes, has a similar mechan-
ism with Co(III)02 hydrogen abstraction as an initiating step. The resulting
phenoxy radical oxidizes the cobalt(II) in the presence of O
2
to give a
3.13 Reactions of O
2
and H
2
0
2
73
cobalt(III)-peroxyphenol complex in which the phenol is linked regio-
specifically by ortho or para positions depending on the substituents.
Activation of O
2
by metal coordination is also proposed(
33
) in a study
of the aerobic conversion of ethanol to acetaldehyde catalyzed by the
complex [Cu(bipy)Ph
3
PI] in DMF solution. Inhibition from added phos-
phine suggests dissociation of this ligand must take place before O
2
coordi-
nation. The HO;- formed attacks ethanol to give the reaction products. In
the absence of ethanol, the copper product is [Cu2(bipyh(OHh]I2. Studies
of the oxidation of [Cu(phenht by O
2
in DMF have also been reported. (134)
In reaction with H
2
0
2
, the 1 : 1 complex [Cupy ]2+ has the most effective
catalase activityY35) Second-order rate constant with HO;- is 3.5 x
105 M-
1
S-l at 25C and 0.1 M ionic strength. Reduction of [Cu(phenhf+
by 0;- is important(136) in the catalyzed oxidation of NADH to give NAD+
by H
2
0
2
. Superoxide dismutase and radical traps inhibit the reaction.
Three intermediates are involved(137) in reaction of H
2
0
2
with low-spin
iron(III)-heme in which the heme ligand is attached to an undecapeptide
fragment. At 22C and pH 10.4, initial reaction with H
2
0
2
proceeds at a
rate of 2.15 x 10
3
M-
1
S-l to yield PtFe
4
+0
2
-, which subsequently rear-
ranges before destruction of the heme, P, by a second mole of H
2
0
2
.
Superoxide ion, 0;, has been detected in the Os04-catalyzed H
2
0
2
decomposition.(138) The rate law (36) implies formation of a peroxoosmic
rate = k[H202]o.6[OS04] (36)
acid which is decomposed by OH- to give 0;. Intermediate peroxide
complexes are also involved in the iron(I1I)EDTA-catalyzed reactionY
39
)
Two pathways are detected, with intermediates [Fe(EDT A)(02)]3- and
[Fe(EDTA)(OH)(H
2
0
2
)]2-. The former species decomposes with a rate
of 2.37 x 10-
2
S-l at 25C and 0.1 M ionic strength to give [Fe(EDTA)f-
and superoxide ion.
The cobalt(II) complexes [Co(EDTA)]2- and [Co(HEDTA)r are oxi-
dized(140) by both HO;- and H
2
0
2
with rate constants 5.4 x 10
2
M-
1
S-l
and 5.6 x 10-
5
M-
1
S-l and 5.1 x 10
2
M-
1
S-l and 4.5 x 10-
5
M-
1
s-t,
respectively, at 30C and 0.5 M ionic strength. A radical mechanism involv-
ing 'OH is proposed and no evidence was found for the presence of
inner-sphere complexes between peroxide and the reductants.
Reactions of H
2
0
2
with "[TiO(EDTA)]2-" are complicated(141) by the
existence of a number of structural forms of the complex depending on
the coordination of the EDT A molecule. Uncoordinated arms of the EDT A
ligand assist the associative reaction giving [Ti0
2
(EDTA)]2- as product.
This product can also be found by reaction of [Ti(EDTA)(H
2
0)r with
O
2
at a rate of 1.02 x 10
4
M-
1
S-l kcal mol-
1
and
- 13.2 cal K-
1
mol-
1
) giving first [Ti0
2
(EDTA)r as a transient, which is
74
reduced in an outer-sphere pathway to give [Ti0
2
(EDTA)]2-, which is
itself reduced by [Ti(EDTA)(H
2
0n- with a rate constant of 75 M-
I
S-I
(Mit 7.2 kcal mol-I and as
t
-26 cal K-
I
mol-I) at 25C and 0.5 M ionic
strength.
The dominant pathway(142) in the oxidation of H
2
0
2
by [Ag(bipyh]2+
in HN0
3
media involves [Ag(bipy)]2+ and the equilibrium (37) has been
Kh
[Ag(bipyh]2+ + H+ [Ag(bipy)]2+ + Hbipy+ (37)
examined(143) with a value of Kh of 3.3 x 10-
3
M at 25C and 1.0 M ionic
strength. The reaction (38) proceeds at a rate of 14.4 x 10
4
M-
I
S -I with
aH
t
30kJmol-
1
and as
t
-62JK-
I
mol-
l

[Ag(bipy)f+ + H
2
0
2
--. Ag+ + HOi + Hbipy+ (38)
Oxidation of mandelic acid(144) by H
2
0
2
, catalyzed by Fe
2
+, is only
50% inhibited by the presence of 'OH radical traps and formation of an
active Fe(IV) species may be a possibility. However it is thought more
likely that the uninhibited pathway involves cage reaction of newly formed
'OH radicals. Peroxytungstic acids are formed(14S) in the H
2
0
2
oxidation
of dmso catalyzed by An extensive study(146) of the oxidation of
cobalt(II) by m -Cl-perbenzoic acid in 90% acetic acid media has appeared.
The mechanism is complex involving a second-order dependence on
[Co(II)] and various dimeric and trimeric oxo- and hydroxo-bridged
species, are formed in the course of the reaction.
In acetonitrite solution, transfer(147) of oxygen from [Ru(bipyhpyO]2+
to PPh
3
has been shown to be quantitative by labeling studies. The mechan-
ism involves a synchronous two-electron transfer step with a rate constant
of 1.75 x lOs M-
I
S -I (Mit 4.7 kcal mol-\ as
t
-19 cal K-
I
mol-I) at
26.6C giving[Ru(bipyhpyOPPh
3
f+, which subsequently hydrolyzes to give
free Ph
3
PO.
Oxidation of Ph
4
B+ by [IrCI
6
f- and [IrBr6f- is first order
(48
) in both
oxidant and reductant with rate constants 8.7 x 10 M-
I
S -I (Mit 11.9 kcal-
mol-\ as
t
-9.7 cal K-
I
mol-I) and 74.4 M-
1
S-I (Mit 13.5 kcal mol-\
as
t
-4.4 cal K-
I
mol-I), respectively at 25C and 0.1 M ionic strength.
On the other hand,(149) oxidation of BH';- by [Fe(CN)6]3-- is independent
of the oxidant and involves rate-determining hydrolysis of BHiH+.
Reduction(1S0) of [Co(CN)S]3- by H2 in aqueous media gives the
cobalt(III) hydride complex [Co(CN)sH]3-. A second-order rate depen-
3.14 Miscellaneous Reactions 75
dence on suggests the reactant is [Co
2
(CNhot-, which can be
considered a Co(I)/(III) system. In D
2
0 solution, with H
2
, equivalent
amounts of hydride and deuteride are produced showing that the H2
cleavage is heterolytic. Photolysis of Cr
2
+ in aqueous media gives CrH
2
+,
which reacts with a proton to give H2 at a rate of 1 x 10
4
M-
1
S -1 at 26C
and 0.2 M ionic strength and is much more reactive than the corresponding
derivativeY51) A smaller deuterium isotope effect is noted with
the hydride and a mechanism involving rate-determining O-H rather than
Cr-H cleavage is proposed.
Part 2
Substitution and Related
Reactions
Chapter 4
Reactions of Compounds
of the Nonmetallic
Elements
4.1. Introduction
The general arrangement of material follows that used in Volume 1. As
before, there will be some consideration of topics in the inorganic/organic
overlap region, and some reactions between main group compounds and
transition metal compounds will be discussed briefly,
4.2. Boron
One of the reactions discussed in Volume 1, namely the reaction of
sodium tetrahydroborate with alcohols (other than methanol), was suggested
to involve the intermediate 'BH2 on the basis of the epr spectrum of an
adduct with the spin trap nitrosodurene, (1) The epr spectrum has been
reassigned and attributed(2) to the species DurN(O')BH3Na +, which is
suggested to be formed from reaction of the spin trap with 'BH3 (or possibly
from DurNO + BH
3
), Thus the radical ion must be considered as an
intermediate, although the previously suggested pathway may still be
present as a minor component.
The reduction of hexacyanoferrate(III) by tetrahydroborate and the
alkaline hydrolysis of the latter compound have been studied, (3) The former
79
80 4 Reactions of Compounds of the Nonmetallic Elements
reaction is complex with an 8: 1 stoicheiometry, and is discussed in terms
of a rate law that is first order in [BH
4
] and [H+] and independent of
[Fe(CN)6]3-. However, the kinetic results reported show the reaction to
be first and not zero order in [Fe(CN)6]3-.
Lipscomb's group have continued their theoretical studies on com-
pounds with calculations on the isomerization of the hypothetical
compound B4H4. (4)
The use of lOB labels shows that the exchange of substituents between
1,2,4,3,5-trithiadiborolanes (BXhS3 and (BYhS3 occurs by two routes: an
exoprocess involving bridging substituents and the intermediate formation
of B
2
XYS
3
, which does not result in an exchange of ring boron atoms; and
a slower endo process involving initially sulfur-boron interaction which
does lead to a statistical distribution of the boron isotopes. (5) Similar
techniques have been used to study substituent exchange between the
triazadiborolidine (1) or the thiadiazadiborolidine (2) with either the
H3C CH3

... B B,
H3C CH3
CH3
1 2
dimethyl- or the dibromotrithiadiborolanes, where again bridge exchange
and boryl exchange pathways have been identified.(6)
4.3. Silicon
4.3.1. Silicon Radicals
The study of the reactivity of trialkylsilyl radicals in solution has been
placed on a firmer foundation by the measurement of absolute rate constants
for some reactions of triethylsilyl radicals (generated by the reactions of
tert-butoxyl radicals with triethylsilane), with some organic halides and
benzil. (7) These data show for example, the greater reactivity of EhSr in
halogen abstraction than that of trialkyltin radicals. Kinetic isotope effects
(kH/ k
o
) for the insertion of photochemically generated dimethylsilylene
and methylphenylsilylene into Si-H and O-H single bonds are about 1.3
and 2.1-+ 2.3, respectively.(8) The preferred mechanism for insertion of
silylenes into O-H bonds is shown in equation (1).(8) Other workers have
shown that dimethylsilylene inserts preferentially into O-H bonds of
alcohols compared with S-H bonds in silanes or Si-O bonds in alkoxy-
silanes. (9)
4.3 Silicon 81
:OSi:+ROH r RO-+-H
l /-"-
(1)
The effects on the rates of cleavage of 3-CIC6H4CH2MMe3 (M = Si
or Sn) and 3,5-ClzC6H3CH2SiMe3 of (a) various concentrations of
NaOMe/MeOH, (b) various concentrations of H
2
0 in
NaOH/H
2
0/MeOH, and (c) variation of R from Me to Et, i-Pr and t-Bu
for alkoxide-ROH mixture, are in accord with the known differences in
the mechanisms of reactions of the silicon and tin compounds, and, in the
former case, the separation of the carbanion R - in the rate-determining
step. (10) Base cleavage of the benzyl-silicon bond in PhCHzSiMe2( CH
2
)n OH
(n = 2 or 3) occurs 0.75 and 95-135 times as readily as in PhCH2SiMe3'
The high reactivity of the compound with n = 3 may arise from intramo-
lecular attack of the alkoxide center in the anion PhCH2SiMe2(CH2hO-
on silicon, giving a six-membered cyclic transition stateY!)
Rates of base cleavage of several substituted 2-thienyltrimethylsilane
have been interpreted in terms of the separation of the aryl anions in the
rate-determining step, a view based in part on ab initio calculations on the
acidities of the monosubstituted thiophens. (12) The separation of the Ph
3
Ge-
anion in the rate-determining step in the hydrolysis of R
3
SiGePh
3
in
NaOMe/MeOH has also been postulated. (13) One noteworthy feature of
this study is the presence of an unusually large steric effect, the compound
Me3SiGePh3 undergoing reaction some 1300 times faster than the com-
pound Et
3
SiGePh
3
. Not unexpectedly, very fast reactions are particularly
susceptible to steric effects. It was not possible to decide whether attack
of methoxide is synchronous with or prior to bond breaking, but there was
no evidence for assistance by proton transfer to the leaving Ph
3
Ge - group.
The alkaline solvolysis of triphenylsilane in aqueous acetonitrile shows
deviation from expected behavior due to reaction (2) which results in the
lowering of catalyst concentration. (14)
(2)
4.3.3. Various Substitutions, /somerizations, and Redistributions
The highly sterically hindered organosilicon iodide (Me3SihCSiMe2I
undergoes solvolysis in methanol by an SN 1 process. (15) Phenacyl bromide
reacts with (arylthio)trimethylsilanes, Me3Si-SPh, to give aryl-phenacyl
sulfides and bromotrimethylsilane via the formation of a five-coordinate
silicon intermediate and a rate-determining heterolysis of the Si-S bond.
This reaction shows a remarkably large positive substituent effect (p =
+2.2) and a large negative entropy of activation which serve to emphasize
mechanistic differences from the reactions of thiostannanes. (16)
The inversion at tetracoordinated silicon in nucleophilic media is well
known, and is always of second or higher order with respect to the
nucleophile. It is of considerable interest therefore to note one example
which involves only a first-order dependence on the concentration of the
nucleophile.(17) The mechanism of inversion of compound 3 involves attack
3
of the nucleophile on the 0-0 edge of the tetrahedron to give structure
4, followed by the sequence of five necessary to invert the
chirality of a trigonal bipyrimidal species. Loss of the nucleophile gives
silanes of inverted configuration. The silane 3 has electrophilic properties,
giving 1 : 1 and not 1 : 2 adducts with several nucleophiles. In addition, the
bidentate ligands in 3 are exceptionally well suited to stabilize pentacoordin-
ated silicon. An interesting parallel is shown in the anionic pentacoordinated
silicon species 5, which shows a temperature-dependent 19F nmr spectrum,
4 X= Nucleophile
5 X=F
which provides the first direct evidence for stereomutation of such a
five-coordinate compound by intramolecular ligand exchange. (18) The
exchange rate of compound 5 is independent of solvent or added
nucleophilic solvent, in accord with the noninvolvement of six-coordinate
silicon.
Alkoxyl exchange in redistribution reactions of alkyl alkoxyl silanes
is catalyzed by several interhalogen compounds, notably iodine mono-
bromide, and by iodineY9) Halogen exchange between alkyl halides and
trimethylsilicon iodide is also catalyzed in some cases by iodine. (20)
Detailed stereochemical studies(21) on substitution of some optically
active silanes R
3
SiX by a series of p-substituted aryloxides and by allyl
lithium shows, for a given leaving group, a dependence upon the ion-pair
dissociation of the aryloxides. In the case of reaction with the lithium allyl,
4.3 Silicon 83
complexation of the lithium favors inversion, which is the opposite to that
found for alkyllithiums. This difference has been explained neatly. The
naked allyl anion has valence orbitals of pure p character. Unfavorable
out-of-phase overlap with the leaving group is increased and so rear-side
attack of the nucleophile with inversion is favored. In the case of the
phenoxide, front-side or near-side attack will be determined by the nature
of the p substituent. With p-methoxyphenoxide anion, the oxygen atom
has a high degree of Sp3 character. Unfavorable out-of-phase overlap with
the leaving group is minimized and so front-side attack with retention of
configuration is favored. In contrast, the oxygen atom of the p-nitro-
phenoxide anion has a high degree of sp character, overlap with the leaving
group is possible, and so rear-side attack is favored.
4.3.4. Reactions of (3-Substituted Organosilicon Compounds
Compounds of this type show exceptional enhancement of reactivity
in reactions such as (3). This enhancement has been attributed to inductive
H+
Me3SiCR20H R
2
C=CR
2
+ Me3SiOH (3)
CH30H/H20
effects, vertical conjugative stabilization of the transition state (U-7T), and
to direct nucleophilic attack. Vertical stabilization is claimed(22) to be the
dominant feature in the acid-catalyzed elimination reactions of p-trimethyl-
silyl alcohols, unlike the case for analogous compounds of other Group IV
elements, where additional factors such as leaving group ability are impor-
tant. Of particular significance in this general area are results obtained(23)
using cyclohexyl silyl compounds having conformational restrictions that
allow the separate assessment of inductive and other effects. The com-
pounds 6 and 7 give cyclohexenes as the only product (carried out in 97%
6
trifiuoroethanol). The cis compound 6 only allows the inductive effect to
operate, while the trans-compound 7 should also allow participation of
vertical stabilization and nucleophilic attack. The rates of solvolysis of these
two compounds have been compared with that of the unsubstituted cyclo-
hexyl trifiuoroacetate derivative. The relative ratio at 25C were 1
(cyclohexyl):3.35 x 10
4
(cis):2.47x10
6
(trans). In the case of the cis
compound the activity of the p-silicon atom can only be exerted via the
inductive effect. In the case of the trans compound the two additional
factors may also be important. It is quite clear that the inductive effect is
particularly important, and that the additional effects that are allowed in
the trans compound (whichever one may be operating) are far less
significant.
4.3.5. Aqueous Solutions of Silicates
The complexity of these solutions is demonstrated by a report, based
on the use of 29Si nmr, that presents definitive evidence for the structures
of 11 species present in an aqueous solution of potassium silicate.(24) Five
of these involve a three-membered ring containing three siloxy units, which
contrary to expectation must therefore be stable at high pH. Other species
are a monomer, dimer, and other cyclic or cage compounds that contain
four-membered rings. The 29Si nmr spectrum of tetramethylammonium
aluminosilicate has also been discussed. (25)
4.4. Nitrogen
The time period under review is a vintage one for nitrogen reaction
mechanisms. A large volume of material has appeared, with many excellent
papers that present new facets of old reactions and study new reactions.
A review article(26) on nitrogen nmr has some relevance to reaction mechan-
isms, while other examples are given in this review.
4.4.1. Nitric Acid and Nitration
An improved preparation of peroxonitric acid (HOON0
2
) has been
reported. (27) This involves the reaction of nitric acid or nitronium
tetrafluoroborate with 90% hydrogen peroxide solution, and the transfer-
ence of gaseous peroxonitric acid from the reaction into appropriate solu-
tions with a stream of argon. These solutions decompose to give dioxygen
and nitrite, probably via the peroxonitrate anion, although the involvement
of radical reactions cannot be excluded. The pulse radiolysis of solutions
of nitrate in water or acetone gives N0
3
radicals, through oxidation by the
primary solvent cation rather than by direct reaction. (28)
Reactions of nitric and nitrous acid with hydroxylamine will be dis-
cussed in a later section. The bulk of published work has been concerned
with nitration of organic substrates, such as cinnamic acids(29) and 2-iodo-
1,3,5-trialkylbenzenes.(30) Evidence has been produced(31) to show the
wider generality of the electron transfer role for nitrous acid in the catalysis
4.4 Nitrogen
Ar+NO+ Art + NO
NO + NO; -+ NO+ + NO;
85
(4)
(5)
NO; + Art -+ nitration products (6)
of nitration [equations (4)-(6)]. Thus reaction in sulfuric acid of 1,2,3-
trimethoxy-5-nitrobenzene with nitrous and nitric acids occurs under condi-
tions for which reaction with either acid alone are negligibly slow. It has
the limiting kinetic form which is zeroth order in nitric acid, showing that
the formation of NO is rate determining. The value of the rate constant
is 10
8
times smaller than that of a diffusion-controlled reaction. Thus the
kinetics are clearly analogous to those of the reactions of the N,N- dimethyl-
anilinium ion for which this mechanism was first suggested. (32)
N,N- Dimethyl-p-toluidine, N,N- dimethyl-4-ethylaniline, and N,N-
dimethyl-2,4,6-trimethylaniline 8 react with nitric acid in aqueous sulfuric
acid to form the ipso intermediate with an N0
2
group at the 4 position.
These reactions are inhibited by the nitrous acid scavenger hydrazine,
showing their dependence upon the presence of trace nitrous acid. When
the ortho position is unsubstituted, the ipso intermediate rearranges to give
the 2-nitro product, with rate-determining loss of the proton from the 2
position. The ipso-intermediate for the 2,4,6-trimethylamine 9 is stable for
many hours at 0C(33) and can be isolated as the hexaftuorophosphate. (34)
It undergoes exchange(35) with labeled nitric acid. When species 9 is formed
with H
15
N0
3
, the beginning ofthe exchange with H14N03leads to enhanced
absorption in the 15N nmr spectrum. When 9 is formed from H
14
N0
3
, the
15N-labeled ion formed at the beginning of the exchange gives an emission
spectrum. These results are interpreted in terms of the formation of the
intermediate radical cation 10, the 15N nuclear polarization arising from
NMe2

y
Me
8
NMe2
Me*:. Me
,+ \
I. I
\._,1
Me
10
the partitioning of the radical pair ArMet NO; between combination and
dissociation. A similar chemical polarization of 15N nuclei has been obser-
ved in the para-nitration of N,N-dimethylaniline(36) and used as evidence
for the involvement of radical pairs and for the probable catalysis of the
reaction by nitrous acid, as the extent of polarization increases with condi-
tions favoring such a catalysis. A related study is the chemical polarization
of 15N nuclei in the nitramine rearrangement. (37)
86
4 Reactions of Compounds of the Nonmetallic Elements
A useful general assessment of nitration of a range of substrates in
aqueous nitric acid has been presented, (38) which has centered on the rate
profile for nitration in nitric acid, the limiting rate of nitration when reaction
occurs on encounter, and the rate of reaction of nitronium ions with the
solvent. In this work hydrazine was added when necessary to prevent
catalysis by nitrous acid. New Raman data on nitric acid and d -nitric acid
have been reported. (39)
4.4.2. Nitrogen Dioxide
The conversion of N0
2
to nitric acid [equation (7)] has been much
studied as the rate-determining step in the industrial manufacture of nitric
2N0
2
(g) + H
2
0(l) 2H+ + NO;- + NO
z
(7)
acid. Current concern with this reaction is focused on its role in atmospheric
chemistry, which involves rather different conditions. Recently, therefore,
reaction (7) has been studied(40) at low pressures (1 x 10-
7
PN02 8 X
10-
4
atm) in the search for pathways which would be excluded in earlier
studies. The rate depends upon the transfer of the reactant, the solubility
of N02, and the homogeneous aqueous phase kinetics. Values of H
N02
,
the Henry's law constant, and k, the second-order aqueous phase rate
constant, are (7.0 0.5) x 10-
3
mol dm -3 atm -1 and (1.0 0.1) x
10
8
dm
3
mol-
1
S-1 at 22C.
4.4.3. Nitrous Acid and Nitrosation
The equilibrium constant for reaction (8) has been redetermined(41)
as (3.03 0.23) x 10-
3
dm
3
mol-t, by monitoring a uv band for N
2
0
3
Some
(8)
evidence was found for the formation of a second absorbing species at high
acidity (possibly which may account for the higher value (K =
0.16 dm
3
mol-
1
), reported previously. The fact that N
2
0
3
is formed to a
much lower extent in solution than was previously thought to be the case
resolves an anomaly of long standing in the interpretation of the kinetics
of diazotization of amines by the N
2
0
3
pathway. The apparent reaction
rate between N
2
0
3
and amines is far less than the encounter rate (based
on [N
2
0
3
] calculated with the previous value of K), whereas reactions with
nitrosyl halides were close to the encounter rate. However, if the lower
value of [N
2
0
3
] obtained from K = 3.03 X 10-
3
dm
3
mol-
1
is used, then
the reaction rate (7 x 10
8
dm
3
mol-
1
S-1) at 25C is close to the encounter
rate.
4.4 Nitrogen 87
The nitrosation of aniline by N
2
0
4
in nonaqueous solvents is first order
in N
2
0
4
and zeroth order in aniline, suggesting a rate-determining forma-
tion of NO+ from N
2
0
4
. (42) Propyl nitrite, (43) acetyl nitrite, (44) and nitrosyl-
pentacyanoiron(II) (45) have all been used as nitrosating agents. The last-
named compound reacts with a,8- and a,e -diamino acids to give heterocyc-
lic amino acids under certain conditions. Environmental concern had led
to the study of nitrosation by nitrogen monoxide. N -nitrosamines are
formed rapidly from N -methylpiperazine, morpholine, and piperidine using
NO in the presence of HI or metal iodides. The iodide is oxidized to iodine
by NO with the formation of N
2
0. Iodine then reacts with NO to give
nitrosyl iodide, which appears to be the nitrosating agent. (46)
The thionitrite from 2-acetylamino-2-carboxy-1,1-dimethyl-ethane
thiol (RSNO) acts as a nitrosating agent, but not in the presence of sodium
azide, showing that RSNO acts as a nitrosating agent by hydrolysis, or by
the formation of nitrosyl halides (in the presence of halides). The thiol
RSH is slightly more reactive than hydrazoic acid toward free nitrous acid.
Hydrazoic acid has been regarded previously as the most effective trap for
nitrous acid. The reactivities of the nitrous acid traps hydrazoic acid and
sulfamic acid are in the ratio 29: 1. (47) The relative efficiencies of several
nitrite traps over the acidity range 0.95-3.94 mol dm -3 sulfuric acid and
over a range of [Br -] have been assessed. (48)
Thiourea is an efficient catalyst for the nitrosation of morpholine and
the diazotization of aniline. In the former case the efficiency of
thiourea: SCN- : Br - as catalysts lies in the ratio 4200: 240 : 1. For thiourea
+
this reflects the large equilibrium constant for the formation of the ON -S=
ion from thiourea, rather than a large rate constant for the attack of the
ion upon morpholine. (49) Thionitrosyl compounds have been detected as
intermediates by the use of 15N nmr in the reaction of 15N -enriched nitrite
with thioureas under acidic conditions that give the urea by hydrolysis. In
contrast, under lower [H+], added nitrite gives the N -nitrosothiourea.(50)
Nitrosations of more specialized organic interest include that of 2- and
4-methylaminopyridines and their N -oxides(51) and aminopyridines. (52)
Those interested in diazotization reactions and the behavior of diazonium
ions should read a series of papers on the mechanism of coupling of
diazonium ions, (53) their reduction by free radicals, (54) and the factors
controlling dediazoniation. (55)
Some particularly interesting reactions of nitrous acid with inorganic
compounds have been studied, including that with hydrazine to give
dinitrogen and dinitrogen monoxide via the formation of azide. Tracer
experiments with 15N-enriched hydrazine with excess of nitrous acid have
been interpeted(56) in terms of a cyclic azide intermediate [equations (9)
and (10)]. This accounts for the production of dinitrogen with 29N2 and
NH 0
/ '" /
H2N N
(10)
F
8
N
2
, anddinitrogen monoxide with C
5
N_
14
NO) and t C
4
N_
14
NO). An
alternative view is that scrambling occurs by homolytic fission of nitrosyl-
azide to give NO' and N
3
; the latter species forms N6 (within a solvent
cage), which then decomposes to give scrambled linear N3 which recombines
with NO' to reform nitrosylazide. However, a very recent calculation(57)
shows that N6 is neither thermodynamically nor kinetically stable and that
reports on its apparent existence must be questioned. Accordingly, this
explanation for isotope scrambling does not seem plausible. Other isotopic
work on the hydrazine-nitrous acid reaction, using H
I5
N0
2
, gives N
2
0 and
N2 of isotopic composition predicted for N-atom scrambling via a cyclic
azide intermediate. However, preference is given to the view that this
results from mixtures of products from double nitrosation and linear azide
pathways. (58) On balance, at present, "cyclic azide" seems to be an attractive
but unlikely explanation for the isotopic data.
The yellow species formed in the reaction between sodium nitrite and
thiosulfate in acidic, aqueous solution has been identified as the S-nitrosated
thiosulfate (03SSNOr, which is suggested(59) to be formed by parallel
pathways involving the nitrosonium ion and dinitrogen trioxide. The much
studied reaction between nitrite and sulfite to give hydroxylamine disulfon-
ate has received further attention(601 and some apparent discrepancies have
been clarified. For the pH range 4.5 to 7 the rate equation is given by (11).
rate = k
o
[H+]2[NO
z
] + k
1
[H+][NO
z
][HS0
3
] + k
2
[NO
z
][HS0
3
f (11)
The term first order in [HS0
3
] is usually dominant, while the [HS0
3
]2
component only becomes important at pH values greater than 6.5 and
bisulfite concentrations greater than 0.1 mol dm -3. The latter pathway is
suggested to involve direct attack of nitrite on metabisulfite.
The rate of oxidation of formic acid by nitrous acid in concentrated
perchloric acid increases with [H+] until about 7.3 mol dm -3 when there
is a sharp decrease in rate with further increase in acidity. (61) Similar
behavior observed for the reaction in nitric acid has been attributed to the
conversion of HN0
2
into N
2
0
4
, a suggestion that now seems incorrect in
light of the current work. An explanation for the results in perchloric acid
is difficult to find, and it is tentatively suggested that the reactivity of formic
acid toward NO+ is reduced by hydrogen bonding.
4.4 Nitrogen 89
Oxygen exchange in doubly labeled nitrite 15N
18
02" has been success-
fully followed by 15N nmr.(62) The presence of 180 results in an up-field
shift in the 15N nmr resonance of Na
15
N0
2
, thus allowing the direct study
of oxygen exchange. This process has previously only been studied with
difficulty. Nevertheless, the present data support the conclusion that in
dilute nitrite solutions this exchange occurs through the nitrous acidium
ion H
2
NO;, although it is not clear whether this involves direct nucleophilic
attack by water on the nitrous acidium ion, or the formation and rehydration
of NO+.
Reactions of nitrite with transition metal species that have been studied
include those with vanadium(V), (63) tris(3,4,7 ,8-tetramethyl-1, 10-
phenanthroline )iron(II), (64) and iron(II). (65) In the last case nitrite is reduced
sequentially at pH 5 to NO and N
2
0. Below about pH 4, the species
FeN0
2
+ is stable against reduction to N
2
0. Above pH -8 further reduction
to N2 occurs. The formation of nitropentaminecobalt(III) from the aquoam-
mine complex and nitrite involves nitrosation by N
2
0
3
.(66) Oxygen-17 nmr
studies(67) on the isomerization of the complex to the nitro form show that
spontaneous 0-0 exchange occurs at a rate comparable to spontaneous
O-N isomerization, suggesting that aquation of the nitrito group occurs by
a mechanism other than loss of NO+. Thus two reactions, one apparently
the reverse of the other, take place by quite different pathways!
4.4.4. Trioxodinitrate and Nitrogen Monoxide
The thermal decomposition of solid alkali metal trioxodinitrates is
suggested to involve the intermediate formation of hypo nitrite. (68) The 15N
nmr spectrum of the trioxodinitrate anion shows(79) that protonation occurs
at the "nitrosyl" nitrogen atom as in equation (12). This observation has
important mechanistic implications, as the trioxodinitrate ion decomposes
to nitrite and dinitrogen monoxide via the monoprotonated anion. N-
protonation results in cleavage of the N-N double bond (and ultimately
the formation of HNO and N0
2
). This accommodates the known reversibil-
ity of this reaction, which would be difficult to understand if cleavage of
N =N took place, as this would necessitate recombination of HNO and
N02" via diradical species. It is also important to note that the decomposition
gives HNO not NOH.
90
4 Reactions of Compounds of the Nonmetallic Elements
Decomposition of sodium trioxodinitrate in the presence of
[Ni(CN)4f- gives [Ni(CNh(NO)]2- by direct displacement of CN- by NO-.
The NO- produced by the reaction between nitrogen monoxide and
hydroxylamine is also trapped by tetracyanonickelate(II) in a direct dis-
placement reaction, but the trapping efficiency differs in the two cases. This
may reflect the difference in the electronic states of NO- formed in the
two reactions, NO- from HNO being a singlet species and NO- from NOH
being a triplet. (70)
The redox chemistry of nitrogen monoxide has attracted further atten-
tion partly in an environmental context. It is reduced by Fe(II) to give
HNO and hence N20. Further reduction to N2 does not occur below
pH 8.(65,71) The first stage is the formation of the Fe(II) nitrosyl complex,
for which equilibrium and kinetic data have been reported by two research
groups. (71,72) Formation of this species is enhanced by bonding of acetate
to Fe(II), There is also evidence(72) for the formation of a dinitrosyliron(II)
species which plays a role in the reduction of NO by Fe(II), This nitrosyl
species may involve NO+ and NO- groups in a formal sense, but there are
no definite conclusions available at present.
The reaction of nitrogen monoxide with ammonia to give dinitrogen
and dinitrogen monoxide is catalyzed by dinitroalkyldiamine complexes of
cobalt(III),(73) Reduction by tin (II) gives dinitrogen monoxide, with
dinitrogen as a minor product. A tin(II) nitro so hydroxylamine species is
suggested to be an intermediate, while the production of N2 may result
from reaction with a second Sn(II),(74)
4.4.5. Hypo n itrite
Hyponitrite shows many similarities with trioxodinitrate, including
decomposition through the monoprotonated anion. It is rather surprising
therefore that HN
2
0;-, unlike HN
2
0
3
, is oxygen protonated, and that the
mechanisms of decomposition of HN
2
0;- and HN
2
0:3 are therefore quite
different. (75)
4.4.6. Dinitrogen Complexes
The mechanism of formation of hydrazido(2 -) complexes from
dinitrogen complexes by reaction with acid in THF, (76) and the formation
of organonitrogen compounds(77) have been discussed.
4.4.7. Azide
Reference to azide as an intermediate in the hydrazine-nitrous acid
reaction has already been considered. On balance, it was felt that cyclic
4.4 Nitrogen 91
azide was unlikely to be formed. Isotope scrambling does occur(78) with
15N -labeled azide and p-toluenesulfonyl azide, possibly through the revers-
ible formation of the N-pentazole derivative [equations (13) and (14)].
TsN
3
+ 15N=N=N- ..... Ts-N-N=N-
15
N=N=N (13)
TsN-N=N-
15
N=N=N
TsN3 + N=15N=N-
TsN--N 151
\ ---N
N
=-- - 15
Ts-N-N=N-N= N=N
(14)
Micellar-bound azide ion shows a remarkably high nucleophilicity, probably
reflecting the charge distribution in the anion. (79) Azide quenches singlet
oxygen via formation of azide radical. (80)
4.4.8. Nitroamine and Hydroxylamine
Nitroamine(NH
2
N0
2
) is reduced by vanadium(II) to give dinitrogen,
while reduction with chromium(II) is a six-electron process giving dinitrogen
and ammonia. (80a) The redox chemistry of hydroxylamine has attracted
attention, including kinetic studies on its reaction with iodine(80b) and
Fe(II)/Fe(III).(81) Of particular interest are data on the decomposition of
hydroxylamine in nitrous and nitric acids(82) (important in the context of
the reprocessing of nuclear fuel). The reaction with nitric acid has a complex
stoicheiometry. Nitrous acid and dinitrogen monoxide are products, and
nitrous acid is an essential catalyst. Under certain conditions hydroxylamine
reacts with nitrous acid to give dinitrogen monoxide. Nitrite generation
takes place by reaction (15). The overall mechanism is in Scheme 1. The
NH
3
0H+ + 2HN0
3
..... 3HN0
2
+ H30+ (15)
rate of formation of N
2
0
4
controls the production of nitrous acid, while
Scheme 1
H+ + HN0
2
+ NO)" N
2
0
4
+ H
2
0
N20 4 + NH20H -+ HNO + N
2
0
3
+ H
2
0
N
2
0 4 + HNO -+ HN0
2
+ N
2
0
3
N20 3 + H
2
0 -+ 2HN0
2
scavenging of nitrous acid increases with [NH
3
0H+]. The nitrite formation
and decay reactions thus have different relative importance at high and
low [NH30H+]. Formation of nitrite is favored by increase in [HN0
2
],
decrease in [NH
3
0H+], and increase in temperature.
Several queries on the: mechanisms of these reactions have been
raised. (83) The reaction with nitrous acid has been well studied previously. (84)
This shows an interesting dependence on acidity, the reaction rate increasing
with [H+] and then, at about 2 mol dm -3 [H+], showing a marked decrease
with increasing [H+]. The mechanism is shown in Scheme 2, where the
Scheme 2
H+ + HN0
2
NO+ + H
2
0
NO+ + NH
3
0H+ NH
3
0NO+ + H+ A
NH
3
0NO+ --+ ONNH
2
0H+ B
ONNH
2
0H+ --+ HONNOH + H+
cis-H
2
N
2
0
2
N
2
0 + H
2
0
trans-H
2
N
2
0
2
--+ N
2
0 + H
2
0
change in dependence on acidity is suggested to result from a change in
rate-determining step from the nitrosation step (A) to the transfer of the
NO+ group from oxygen to nitrogen (B), on which an ionic strength effect
is imposed to account for the decrease in rate with increase in acidity.
Bennett et at. have shown(83) that this variation in observed rate
constant with acidity may be described by a function of the form C(aH+)/(1 +
d(aH+) + f(aH+)2), where coefficient d is close to zero. They accept that
the scheme is essentially correct, but as experimental results differ from
those predicted by the model at high acidity, they suggest that some
modification of the scheme is necessary. However, their treatment of the
mechanism seems to be deficient in that, implicit in their treatment, is the
assumption that HN0
2
is converted substantially to NO+ at acidities around
2 mol dm -3 [H+], which is not the case. An alternative reassessment(85) of
the acidity dependence involves the insertion of an additional step into
Scheme 2, and the assumption that transfer of the nitroso group from
oxygen to nitrogen only takes place in the free base [equations (16) and
(17)]. A steady state treatment then gives a rate law consistent with the
NH
3
0NO+ NH
2
0NO + H+ (16)
(17)
4.5 Phosphorus and Arsenic
93
expression derived by Bennett et al. The modified Scheme 2 also allows
the interpretation of kinetic isotope effects of long standing, (84) which show
a change in kD/kH from -2 to -7 at acidities corresponding to the two
rate-determining steps.
Bennett et al.(83) also claim that the nitric acid oxidation of hydroxyl-
amine gives dinitrogen in addition to the products described previously.
This is attributed to the reaction between hyponitrous acid and nitrous
acid, which seems unlikely. Nevertheless, this is an interesting observation,
and clearly there is considerable scope for the use of 15N labels in sorting
out these problems of stoicheiometry and mechanism.
4.4.9. Hydrazine
Most work has centered on the oxidation of hydrazine and organo-
hydrazines; the latter topic has been reviewed. (86) Autoxidation of 1,1-
dimethylhydrazine gives some 24 identified products!(87) Hydrazine is oxi-
dized to dinitrogen and ammonia by peroxodisulfate in an Fe(III)-catalyzed
reaction, (88) and to dinitrogen by carboxylato-bound chromium(V) via the
rate-determining formation of diimine N
2
H
2
.(89) The hydrolysis of acyl-
hydrazine in sulfuric acid solution changes from an A2 mechanism to an
Ai mechanism at high acidity. (90)
4.5. Phosphorus and Arsenic
4.5.1. Phosphorus(Vj Compounds
Peroxomonophosphoric acid (PMPA) oxidizes anthranilic acid and
p-aminobenzoic acid in aqueous acid to the azoxy compounds, via
nucleophilic attack of the unprotonated nitrogen group on the peroxo
oxygen. (91) The same authors also report on the oxidation of 3-
aminopyridine by PMP A. (92)
The formation and chemical properties of monomeric metaphosphates
have been discussed. (93-95) These are of considerable interest in a bio-
chemical context, and generally as reaction intermediates in the hydrolysis
of phosphates. The ready conversion of metaphosphate to orthophosphate
probably does not reflect the essential instability of the three-coordinate
phosphorus(V) species, but the greater relative stability of orthophosphate.
Kinetic studies have been carried out on the hydrolysis of phenyl
phosphatosulfate as models for the enzymatic hydrolysis of compounds
with P-O-S linkages. These compounds are involved as intermediates in
biological sulfur metabolism. The hydrolysis of phenyl phosphatosulfate is
catalyzed by Mg2+, which activates the P-O-S link towards nucleophilic
attack by imidazole, and enhanced by micellar conditions. (96) The hydrolysis
of the phosphonamides 11-13 involves the rate-determining cleavage of
(]
11 12
the P-N bond, with an SN2(P) mechanism.(97) These compounds are more
reactive than carboxylic amides, a phenomenon which has been attributed
to the different sites of protonation. The latter compounds are O-proton-
ated, giving a delocalized cation with high resonance stabilization. Addition
of water as a nucleophile destroys this situation and so hydrolysis is slow.
Phosphorus amides are N -protonated, with a good leaving group. (97) The
oxidation of (4-hydroxyphenyl) phosphoric acid by cerium(IV) to give
quinone and phosphate has been investigated. (98)
Several interesting studies on reactions of cyclophosphazenes have
been reported. Reaction of t-butylamine with N
3
P
3
CI
6
and N
4
P
4
Cl
8
in THF
occurs via an SN2(P) mechanism, with a five-coordinate phosphorus inter-
mediate. The greater reactivity of the tetramer was explained in terms of
steric effects.(99) A study of the reaction of N
3
P
3
CI
s
(NRR') with dimethyl-
amine shows that the steric effects associated with a range of Rand R'
groups are very small indeed. (100) The latter workers have divided amination
reactions into three classes, in an attempt to accommodate apparently
contradictory work on the importance of steric effects. These classes are
(i) nongeminal substitution relative to a given amino substituent (Le.,
substitution at a =PCh center), where the substituent is far away from the
reaction site and so has little effect; (ii) geminal substitution with a primary
amino substituent, where a conjugate base mechanism operates with a
three-coordinate intermediate that is not sensitive to steric effects; and (iii)
geminal substitution with secondary amines, where there is strong steric
inhibition. In addition it should be noted that electronic effects cannot be
ignored.
4.5.2. Phosphorus(IIIj Compounds
Reports on the conversion of P(IIl) compounds to P(V) compounds
have been published, namely, oxygen transfer to phosphines by
[(bipyhpyRuO]2+ (101) and the rearrangement of an acetyldiorganophos-
phine to an acyldiorganophosphine oxide. (102) The Michaelis-Arbuzov
rearrangement has been reviewed.o
3
) The first stage in the reaction of
phosphites with alkylhalides in the Michaelis-Arbuzov rearrangement is
nucleophilic attack of the phosphorus. An interesting contrast is seen in
4.6 Oxygen
95
the reaction of trialkyl phosphite with trimethylsilyl iodide to give 0-
trimethylsilyl-esters of alkylphosphonic acid, where the first step is the
formation of the iodophosphite in a four-center reaction where the P(III)
center behaves as an electrophile.(104)
Phosphite reacts with hydroxyl radicals or hydrogen atoms to give phos-
phite radicals P0
3
which react with thiols and disulphides [equations
(18) and (19)]. At higher concentrations of phosphite a chain reaction is
established for reaction (19), based on the reformation of phosphite radicals
in the reverse of (18).0
05
)
P0
3
+ RSH RS' + HP0
3
2
- (18)
+ RSSR --+ + RS' (19)
4.5.3. Phosphorus(I) Compounds
The reactions of hypophosphorus acid with silver(II)(106) and
silver(I)(107) have been reported.
4.5.4. Arsenic Compounds
The rate of hydrolysis of arsenate(V) triesters OAs(ORh is much faster
than that of phosphate triesters, and decreases in the order R = Me, Et,
n-pentyl, and isopropyl. Rate constants for the first hydrolysis have been
measured, and estimated for the second stage. The third step could not be
followed by use of the stopped flow technique. Studies in solvent-water
mixtures with varying water concentrations confirm the involvement of
water in the rate law. An associative mechanism is postulated(108) with a
five-coordinate intermediate OAs(ORh(OH
2
).
4.6. Oxygen
Much attention has been paid to the chemistry and biological chemistry
of singlet dioxygen and superoxide ion. The lifetime of the former species,
known to be solvent-dependent, is much increased for deuterated acetone,
acetonitrile, benzene and chloroform compared to the undeuterated sol-
vent. This is a remarkable solvent deuterium isotope effect.(109) Electron
transfer to 10
2
from tetramethylphenylenediamine to give superoxide has
been confirmed, the rate of reaction being close to the diffusion-controlled
limit.(llO) Kinetic studies on the photochemical formation of superoxide
from lL-superoxodecacyanodicobalt(III) ions(1l1) and oxygenated ethanol
solutions(1l2) have been reported.
The proton-induced disproportionation and the oxidation of super-
oxide have been assessed with respect to the conditions necessary for the
d
f' I . I d' (113 114) Th d'
pro uctlOn 0 SlOg et or tnp et state loxygen. e Ispropor-
tionation in strongly acid conditions is of second order with respect to [02"],
but with less acidic systems such as phenols and water the rate is first order
with respect to superoxide and to acidic reagent, proton transfer being the
d
. . (115)
rate- etermmmg step.
The superoxide ion has been cited as a major factor in the toxicity of
methyl viologen (MY) or paraquat. The radical cation Myt is suggested
to react with dioxygen to give superoxide. It now appears(116) that super-
oxide forms a diamagnetic adduct with the methyl viologen radical cation,
MY+02" which then rearranges. This peroxide intermediate may be highly
active biologically. Other superoxide-radical couplings have been reported
with flavins. (117)
The decay of the ozonide radical ion in aqueous, alkaline solution has
been characterized.(l1S) A complication arises from carbonate impurities
in the alkaline solution, which are converted to CO)" radical ions in the
pulse radiolysis experiments. The ozonide radical ion 0)" (formed by
reaction between 0- and O
2
) reacts with the carbonate radical ion to give
ozone and carbonateY
l9
) This may explain why carbonate has a stabilizing
effect on ozone, as both 0)" and CO)" radicals have been detected during
the decomposition of ozone in alkaline solutions with carbonate present, (120)
and this reaction between the two radical species may occur. The mechanism
of formation of hypobromite from ozone and bromide has been
studied. (121)
Many of the reactions of hydrogen peroxide reported on during the
period of this review fall outside the scope of this chapter. For completeness,
however, note should be taken of the reaction of peroxide with the following
metal species: Os(YIII) (122,123); alkoxo-bridged binuclear complexes of
Mn(III) (124); ethylenediaminetetraacetato- and N -(2-hydroxyethyl)ethyl-
enediamine-N,N' ,N'- triacetato complexes of Co(II), (125) bis(2,2'-
bipyridine )silver(II), (126) ethylenediaminetetraacetatoiron(III) (127); and
copper(II)/pyridineY2S) The Os04-catalyzed decomposition involves the
production of superoxide. (122)
The oxidation of dimethylsulfoxide by hydrogen peroxide is catalyzed
by sodium tungstate, probably through the formation of peroxytungstic
acids H2 W0
5
and H2 wO
s
Y29) The iron(II) sulfate-catalyzed decomposi-
tion of hydrogen peroxide shows oscillating evolution of dioxygen, provided
that heterogeneous effects are reduced by hydrophobic coating of glass
surfaces. The amplitude of these variations may be as high as 20% of the
mean rate with periods of about one minute. The effect is ascribed to the
finite lag time between nucleation and escape of bubbles. (130)
4.7 Sulfur
97
Reaction between peroxide and chlorine compounds has attracted
attention in the contexts of the production of singlet dioxygen and, interest-
ingly, in cellular disinfection mechanisms in living organisms.(131) The rate
of oxidation of hydrogen peroxide by compounds XCI is first order in [XCI]
and [HOzl These compounds contain chlorine in the +I formal oxidation
state, namely, tert-butyl-hypochlorite, N -chlorosuccinimide, ethanol
chloramine. Production of singlet dioxygen was detected in reactions of
the first two of these compounds, and arises from reaction between HOZ"
and HOCI produced from XCI. (132) It should be noted that HOi reduces
Ch at a rate close to the diffusion-controlled limit, and so should also be
considered when formulating free radical mechanisms for the reaction
between chlorine and hydrogen peroxideY33) Understanding of the very
complex reactions between hydrogen peroxide, iodine, and iodate over a
wide concentration range, particularly for the nonosciIIatory decomposition
of hydrogen peroxide, (134) has been advanced.
Reactions of hydroxyl radicals continue to be well studied including
those with diethyl ether(135) and methionineY36) Reactions of inorganic
interest are those with Ni(II) macro cyclic complexes (which give either
ligand radicals or ligand radicals plus Ni(III)), (137) ozone/
13B
) and coordin-
ated azide. (139) In the last case, oxidation of [Co(NH
3
)s(N
3
)]2+ with hydroxyl
radical gives an intermediate radical of surprising stability, which is pre-
sumed to be [Co(NH
3
)sNNNOHf+. This decomposes by a first-order
intramolecular redox reaction to give Co(II), N
2
, and N
2
0. The dinitrogen
monoxide arises from NOH produced in the decomposition.
4.7. Sulfur
4.7.1. Oxidation with Peroxo Acids of Sulfur
An acid-catalyzed pathway has been identified in the oxidation of
iron(II) by peroxodisulfate by studying this well-characterized reaction over
a wider acidity range. (140) The oxidation of nitrilotriacetatocobalt(II) by
this reagent has also been examined. (141) Many reactions of peroxodisulfate
are catalyzed by metal ions, through the formation of their higher oxidation
states. However, doubts have been expressed(142) over previous work that
assigns this mechanism to the catalysis by Cu(II) of the malic acid-
peroxodisulfate reaction.
The decomposition of peroxomonosulfate, equation (20), is catalyzed
by the dual catalysts Ag + and with a rate law that is first order in
both catalysts only, while both oxygen atoms in the dioxygen product are
2HSOs 2HSOi + O2
(20)
derived from the terminal peroxo oxygen in HSO
s
. The rate-determining
step is the oxidation of Ag+ by the Ag2+ then reacting with HSO
s
to give an HS0
5
intermediate. This rapidly decomposes in parallel,
bimolecular pathways to give (0
2
+ 2S04") and (0
2
+ The
decomposition is also catalyzed by C0
2
+, the mechanism being one in which
C0
2
+ and HSO
s
replace Ag+ and respectivelyY43)
Peroxomonosulfate oxidizes Y02+, the SO; radical ion being involved
in the mechanismY
44
) The oxidation of peroxovanadium(Y), YO;, by
HSO s is catalyzed by Y02+, with a rate law rate = k 1 [HSO s][Y0
2
+]o,
kl being the rate constant found for the Y02+ /HSO
s
reaction. It is
suggested that SO;, formed in the rate-determining step, oxidizes YO; to
the Y0
3
?+ radical cation, which then decomposes to give Y02+ and O
2
.
The formation of the radical cation Y0
3
?+ is intriguing, as it implies a
one-electron oxidation of the peroxo complex. (145) Dimethylsulfoxide is
oxidized by peroxomonosulfate via species HSO
s
and SO;-, the latter
species being more reactive. The mechanism is one of nucleophilic attack
by the peroxide on the sulfur atom in DMSOY46)
4.7.2. Reactions of Oxo Acids of Sulfur
The kinetics of oxidation of thiosulfate to tetrathionate by
[Os04(OHh]2- (for uncatalyzed and [Fe(CN)6]3--catalyzed paths) involves
the rate-determining decomposition of an intermediate complex
[Os04(OH)(S203)]3-.o47) An important contribution to the chemistry of
sulfite species is the redetermination of the equilibrium constant for the
dimerization of bisulfite ion to give (K = 0.088 dm
3
mol-
1
at 25C
in 1 mol dm-
3
NaCI0
4
). This is quite different from previous values. This
Raman work has also produced evidence for an isomer of HS0
3
with H+
attached to oxygenY48) Copper(III) tetraglycine oxidizes sulfite in two
reversible one-electron steps to give aquated S03 via a sulfite radical anion
intermediate. (149) A series of papers on the reactions of sulfito complexes
has been published.o
50
)
4.7.3. Decomposition of a Sulfur Nitroso Compound
(S-Nitrosothiouronium Ion)
A transient red color observed during the oxidation of thiourea by
nitrous acid to formamidine disulfide [(NH
2
hCSSC(NH2hr+ is the S-
nitroso compound [(NH
2
hCSNOt. The decomposition of this intermedi-
ate, equation (21), involves two pathways, one involving the reversible
2(NH
2
hCSNO+ -+ (NH
2
hCSSC(NH
2
h + 2NO (21)
4.9 Halogens 99
formation of a radical intermediate [(NH
2
hCSSC(NH
2
h]t from thiourea
and the nitroso compound, and the other a bimolecular reaction between
two moles of the nitroso compound. (151)
4.8. Selenium and Tellurium
4.8.1. Oxidation of Selenium(lV)
The oxidation of selenium(IV) to selenium(VI) by Ce(IV) is suggested
to involve the formation of a 1 : 1 complex and an Se(V) intermediate. (152)
The reaction is catalyzed by ruthenium compounds, via the formation of
Ru(VIII) species. (153)
4.8.2. Tellurium Compounds
125Te nmr has been used to study exchange between diarylditellurides,
equation (22). These ditellurides react with dioxygen-producing radical
species, which may be involved in the exchange reaction. (154)
(22)
4.9. Halogens
Much of the work published on halogens has been concerned directly
or indirectly with oscillating reactions. Thus while a separate section is
devoted to oscillating reactions the distinction is not clear cut. Overlap
with earlier sections is also inevitable.
4.9.1. Fluoroxysulfate
The general chemistry of this powerful oxidizing and fluorinating agent
is now being established. Reports are available on its use as an electrophilic
fluorinating agent with aromatic compounds(155) and on some thermody-
namic measurements. (156) From a mechanistic viewpoint it is interesting
that S04F- only oxidizes some species slowly (e.g., Mn2+, Ce3+, C0
2
+,
V0
2
+) and others not at all (e.g., Cr3+). However, silver(I) serves as an
effective catalyst in these reactions (in an analogous fashion to the per-
oxodisulfate case) and so provides a useful extension of the range of
compounds which may be oxidized by fluoroxysulfate. It is clear that,
despite its oxidizing potential, this reagent shows an enormous selectivity
to reducing substrates which is not yet fully understoodY57)
4.9.2. Chlorine Compounds
A potentially useful method for the generation of chlorine dioxide by
the pulse radiolysis of chlorite solutions suffers from the drawback that
hypochlorite is also produced through the reaction of the solvated electron
with chlorite [equation (23)]. This can be overcome to some extent by
eaq + 2CI02" + H
2
0 --+ CIOi + ClO- + 20H- (23)
generating CIOi under pH conditions greater than 8.5, so that the less
reactive hypochlorite is formed rather than hypochlorous acid. (158) Chlorine
dioxide is also formed by the disproportionation of chlorite, a key reaction
in this being the fast reaction between chlorite and hypochlorous acid
[equation (24)].(159) The amount of chlorine dioxide formed depends on
HOCI + 2HCI0
2
--+ 2ClOi + Cl- + H+ + H
2
0 (24)
the acidity and the conditions of mixing. Kinetic studies on the dispropor-
tionation of chlorous acid are simplified if ortho-toluidine is present as
chlorine reacts more rapidly with o-toluidine than with chlorous acid. The
rate-determining step in the presence of added chloride is the production
of hypochlorous acid by reaction between chloride and chlorous acid.
Chlorite ion oxidizes iodine to iodate, a well-known "clock reaction,"
equation (25). The proposed mechanism postulates the intermediate ICI0
2
,
5CI02" + 212 + 2H
2
0 --+ 5Cl- + 4103" + 4H+ (25)
formed by reaction of chlorite with 1
2
, 1
2
0H-, and IOH;Y60) Other
reactions of chlorite to be investigated are those with [Fe(CN)6t-,(161) and
the iron(III) complex of deuteroporphyrin IX (162) to give hyperoxidized
reaction intermediates.
Hypochlorous acid, already discussed in several reactions, has also
been studied in its reactions with morpholine-borane, (163) a-amino
acids,(164) acetone (a method to give pKa values of ketones),(165) and
ethylenediaminetetraacetatotitanium(III) and hexacyanoferrate(II).(166)
A most useful analysis of the various chloramines (and broamines)
formed by mixing aqueous halogen and ammonia solutions is availableY67)
4.9.3. Bromine Dioxide
Most material on bromine compounds is discussed under oscillating
reactions. Pulse radiolysis of aqueous solutions of bromate gives the dioxide
BrOi. This is reduced by hexacyanoferrate(1I) and phenoxide in clean, fast
reactions. Reductions by manganese(II) and phenol are slower and more
complex as complications arise from dimerization of BrOi to give Br204,
4.9 Halogens 101
which is the active species. Thus the formation of the dimer is rate determin-
ing (in the case of phenol) or partly rate determining [in the case of
Mn(II)]Y68)
4.9.4. Iodine Compounds
Oxidation by pedodate of octacyanotungstate(IV) (169) and
chromium(III) (170) has been reported. The latter reaction involves a second-
order dependence on Cr(llI), interpreted in terms of an inner-sphere
mechanism in which I(VII) bridges two Cr(III) centers.
Species containing iodine in formal oxidation six have been formed
by photolysis and radiolysis of aqueous iodate and periodate, equations
(26)-(29). The products formed in (28) and (29) depend upon pH, being
10
3
+ 0- ---.
10
3
+ 'OH ---. 10
3
+ OH-
IO; + e ---.
10; lci
I
+ 0-
(26)
(27)
(28)
(29)
and 10
3
(3 < pH < 7); HsI06" and (8 < pH < 11) and
and (pH> 12). The redox reactions of the I(VI) species are fast
compared with interconversion of the various species. The decay of 10
3
differs from the other I(VI) speciesY71)
The oxidation of iodide by the following complexes has been studied:
[AuCI
4
r, [AuBr4r;(172) Ni(III);(173) Cu(III);(174) together with the redox
reactions of G and (SCN); radical ions with tris(2,2'-bipyridine) complexes
of Os(1I) and Os(III)Y
7
S) The oxidation by iodine of N -acetylmethionine
methyl ester is catalyzed by carboxylic acid buffers, in a complicated reaction
involving the formation of a carboxylic acid anhydride.(176)
4.9.5. Oscillating Reactions
Several theoretical studies have attempted to relate the period of an
oscillating chemical reaction to parameters such as the rate constants in
the kinetic model.(177-179) Aspects of theoretical models for the Belousov-
Zhabotinskii (B-Z) reaction have been discussed. (180-185)
4.9.5.1. Reactions with Bromate, Particularly the B-Z Oscillator
The following bromate oscillators have been discussed: bromate/oxalic
acid/H
2
S0
4
/Ce(IV /111) or Mn(III/II);(186) bromate/catechol/H
2
S0
4
;(187)
bromate/ferroin/H
2
S0
4
;(188) and bromate/Br-/Ce(IV)/(III)Y89.190) Some
particularly interesting results were found for the last example,(190) as
previous ca1culations(191) on stirred tank reactor systems for bro-
mate/Br - / Ce(IV /111) had described the conditions under which bistability
is found, and also predicted the existence of a very narrow region of
small-amplitude oscillations. These oscillations have now been observed
experimentally(190) and so provide useful support for the Noyes' mechanism.
The sensitivity of this oscillator system to small differences in conditions
is shown by the fact that the changing of nominally identical input tubes
in the flow system can significantly change the region of oscillation.
4.9.5.2. Reactions with Iodide, Particularly the B-R Oscillator
The Briggs-Rauscher reaction (acid/iodate/H
2
0
2
/Mn
2
+ /malonic
acid/starch) is a dramatic oscillating system, showing well-defined changes
(colorless-yellow-black-colorless) with several repeat sequences. The
iodate/H
2
0
2
/Mn
2
+ subsystem has been examinedY92) When all three
components are present, 0.002 mol dm -3 [Mn2+] catalyzes the oxidation
of peroxide by iodate at a rate about 10
3
times that in the absence of
catalyst. This is explained by assuming that the radical '10
2
is slow at
abstracting H atoms from H
2
0
2
, but is an effective oxidizer of Mn2+ by
electron transfer. Addition of malonic acid to this subsystem causes oscillat-
ing behavior,(193) and the mechanism has been explored by the addition of
a range of organic and inorganic compounds. A skeleton mechanism has
been outlined(194) which involves 11 pseudoelementary processes. The rate
constants of seven of these processes are known, so clearly considerable
advances are now being made. Substitution of methylmalonic acid for
malonic acid has been carried out.(195)
Another noteworthy achievement(196) is the report of a systematically
designed oscillating system, in which two autocatalytic subsystems, arsenite-
iodate and chlorite-iodide, were linked in a continuous flow stirred-tank
reactor. These two subsystems have been studied independently of each
other. The arsenite-iodate subsystem has been thoroughly examined in a
CSTR and shown to exhibit bistability under a range of conditionsY97,198)
The oscillations of iodide concentration involved a variation by a factor of
more than 105 during each oscillation! In an unstirred system, well-defined
waves were observed. (199) The chlorite-iodide reaction has also been
studied. (200)
4.9.5.3. Miscellaneous Oscillating Reactions
A chlorite-thiosulfate system showed oscillations in a CSTR, and is
the first chlorite-based oscillator involving no iodine-containing species. (201)
4.10 Xenon
103
Other examples involve hydrogen/platinum/oxyhalide(202) and per-
manganate oxidation of oxalate. (203)
4.10. Xenon
Previous suggestions on the mechanism of hydrolysis of xenon difluoride
have been confirmed. (204) The first intermediate is XeO, which interacts
with water to give hydrogen peroxide. Oxidation of hydrogen peroxide by
XeF
2
has already been investigated, and involves a chain reaction initiated
by reaction between XeO and H
2
0
2
.
Pulse radiolysis(20S) of aqueous solutions of xenon trioxide at pH 8-9,
and of xenate, HXe04, at pH 11-13 gave unstable species with xenon in
the formal oxidation states 5 and 7. Pulse radiolysis and flash photolysis
of aqueous solutions of perxenate gives xenon(IX) com-
pounds. These show similarities to the corresponding iodine species in
oxidation states 4, 6, and 8.
Chapter 5
Substitution Reactions of
Inert Metal Complexes-
Coordination Numbers 4
and 5
5.1. Introduction
As in previous years, this section is dominated by studies on square-
planar palladium(II) and platinum(II) complexes. Much of the work extends
and consolidates accepted ideas on pathways for nucleophilic ligand
replacements, including further emphasis on the crucial effects of solvation.
Running parallel with this work, however, are several lines of investigation
on alternative routes to ligand substitution, including electrophilic attack
and oxidative addition/reductive elimination sequences. As more details
of all these processes emerge, it is clear that the distinction between them
can be quite artificial and a continuum of reaction types probably exists.
This somewhat confusing (from the point of view of classification) situation
is reflected in recent reports on five-coordinate complexes. Emphasis is
moving away from mere structural examinations toward investigations of
their reactions and chemical behavior. The vast majority of ligand substitu-
tion reactions at square-planar complexes proceed through five-coordinate
species, and one issue is whether best to regard some of these complexes
as intermediates, or species for study in their own right. During the period
105
106 5 Substitution Reactions-Coordination Nos. 4 and 5
under review, a number of papers present evidence for structural changes
of the pseudorotation type in some five-coordinate species, and this
considerably broadens the scope of earlier ideas on ligand replacement
reactions.
There has been a great deal of activity recently on isomerization
mechanisms of square-planar compounds. As would be expected, the
growing diversity of reaction pathways for ligand substitution is reflected
by an increase in the number of recognized isomerization pathways, as the
two processes are often related.
A number of relevant review articles have appeared. Their subjects
include the chemistry of antitumor platinum complexes, (1) complexes of
platinum metals with weak donor ligands, (2) and transition metal complexes
of sulfide, selenide, and telluride ligands (which includes much material on
square-planar compounds).(3) A review by Chanon and Tobe(4) on electron
transfer catalysis relates to many reaction types, including ligand replace-
ments at square planes.
5.2.
5.2.1.
Substitution at Sguare-Planar Palladium(II)
and Platinum(II)
Palladium(l/) Complexes
A high-pressure stopped-flow apparatus capable of following reactions
with half-lives down to 20 ms has been used to obtain activation parameters
for the anation reactions of [Pd(Et
4
dien)H
2
0f+ and [Pd(Ehdien)H
2
0]2+.
Even so, the less sterically hindered [Pd(dien)H
2
0]2+ reacts (with Cn too
quickly to allow meaningful results to be obtained. (5) The reactions are
first order in Cl-, and values for the Et
4
dien (EhNC
2
H4NHC2H
4
NEh)
complex are AV:j:, -3.0 0.2 cm
3
mol-l; all*, 13.4 0.4 kcal mol-l; and
AS:j:, -10.71.2caIK-
l
mol-
l
. Values for the Et3dien derivative are
similar, but reaction rates are much greater. The evidence all points to an
associative process, la, being the most accurate description of these impor-
tant anation reactions, with bond formation making the dominant contribu-
tion to the negative values of AV*.
pH measurements have been employed to measure accurately the
equilibria (1) and (2) (triL = dien, Et
4
dien, and Me5dien).(6) The substitu-
tion equilibria (1), are paralleled by the dimerization equilibria (2). The
[Pd(triL)H
2
0]2+ + X- [Pd(triL)Xt + H
2
0 (1)
2[Pd(triL)H
2
0]2+ + x- [{Pd(triL)hX]3+ + 2H
2
0 (2)
stability orders are X- = cr < Br- < r < SCN- < OH-, and X- = r
OH- < SCN- for (1) and (2), respectively. Evidence for such singly bridged
5.2 Substitution at Square-Planar Palladium(//) and Platinum(I/) 107
species, [{Pd(triL)hX]3+ is still quite rare. The Ka values increase in the
somewhat surprising order [Pd(Et
4
dien)H
2
0]2+ < [Pd(dien)H
2
0]2+ <
[Pd(Me
s
dien)H
2
0]2+ .
The hydrolysis kinetics of coordinated esters have been measured by
pH-stat methods for a series of a -aminoacid ester complexes [equations
(3) and (4); L = NH
2
CHRCOOR'; A - = NH
2
CHRCOO-].(7) The results
[Pd(en)L]2+ + H
2
0 -+ [Pd(en)At + R'OH + H+ (3)
[Pd(en)L]2+ + OH- -+ [Pd(en)At + R'OH (4)
reflect the bonding in the complexes: in those cases where the carboxylate
oxygen was likely to coordinate to the metal (e.g., when L was ethyl
glycinate), the ester base-hydrolysis rate was accelerated by between 10
4
and 10
7
times by the complexation. The acceleration was less marked with
sulfur-containing L, where the sulfur atom was more likely to coordinate
instead of the oxygen. A kinetically important ion pairing between the
complex and incoming nucIeophile appears to operate and precedes the
attack on the ester ligand, though a contribution from five-coordinate
species (1) could not be ruled out. The catalytic effect of metal ion on ester
hydrolysis is well known and complexes of other metals have been examined
in the past.
All the previous studies employ chelating ligands on some "nonactive"
sites: the extra stability afforded helps to suppress complicating side-
reactions. This stability is further utilized in a study of solvent effects on
initial states and transition states for square-planar substitution.(8) Continu-
ing their studies on the sterically crowded cation [Pd(Et4dien)CIt, Blan-
darner et al. report that the solvolysis (k 1) term generally dominates, though
use of ligands with a high affinity for Pd(II) (e.g., 1- or thiourea, tu) can
still produce a large direct (k
2
) component. Solubility measurements on
the chloride salt in several methanol-water and dmso-water mixtures allow
Gibbs free energies of transfer to be derived, and these reveal an increase
in the stabilization of the cation by increasing methanol content, presumably
due to the organic, hydrophobic periphery of the Et
4
dien ligand. Interest-
ingly, added salts stabilize the initial state quite as well as the organic
solvents do, but salts destabilize the transition state, where MeOH or dmso
stabilize it.
)Q
/0
: Pd
""L
2
A kinetic study on the replacement of L in [Pd(Fo)L] (2) (Fo is
1-(2-hydroxyphenyl)-3,5-diphenylformazan; L = NH3 or py) by various
nucleophiles in seven solvents revealed the usual two-term rate law under
pseudo-first-order conditions.(9) Although the entropy of activation indi-
cated the reactions to be associative in nature, the rigidity of this ligand
hindered the formation of stable five-coordinate intermediates and as a
result conferred a high degree of synchronicity on the substitutions. The
rigidity also ensured that no serious geometry change of the transition state
was likely on varying the solvent. Under these conditions, the kl term
depended only on the donor number of the solvent, and was not related
to the transfer free energy of the substrate. The k2 term revealed a
dependence of the entering group nucleophilicity on both solvent and
substrate, supporting the high degree of synchronicity of bond forming and
bond breaking in the transition state. As with the k 1 terms, transfer chemical
potentials of initial states and transition states stayed close together.
The linkage isomerism of thiocyanate ligands bonded to palladium
continues to afford a rich field for study. Structural studies on cis-
[Pd(NCS) (SCN)L
2
] (L = 1-phenyl-3,4-dimethylphosphole) confirm a
greater trans influence for sulfur-bonded thiocyanate, and indicate that
steric considerations of L exert a greater effect than electronic variations
on both the complex geometry and the ligand bondingYO) 31
p
nmimeasure-
ments on [Pd(CNSh(Ph2P(CH2)nPPh2)] (n = 1, 2, or 3) and
[Pd
2
(CNSh(dppmh] (dppm = Ph
2
PCH
2
PPh
2
) reveal signals from well-
defined linkage isomers at -60C, but averaged signals at 25CYl) For the
"A-frame" complex [Pd
2
(CNSh(dppmh], at least, the vtnmr measure-
ments are independent of concentration, suggesting this isomerization to
be intramolecular. 31
p
nmr spectroscopy has also been used to investigate
halide exchange equilibria between [PdX
2
(dppm)] and [Pd
2
X
2
(dppmh].(12)
In noncoordinating solvents, a near-statistical distribution is observed in
less than 5 min.
5.2.2. Platinum(lI) Complexes
A valuable contribution from Groning, Drakenberg, and Elding(13)
makes use of 195Pt nmr spectroscopy in a study of water exchange and
5.2 Substitution at Square-Planar Palladium(lI) and Platinum(lI) 109
dmso solvolysis in [Pt(OH
2
)4]2+. The 195Pt chemical shifts are very sensitive
to 160 to ISO isotopic exchange, and signals were resolved for each combina-
tion of [Pt(OH
2
)4]2+, trans-[PtCh(OH
2
h], and trans-[PtCh(OHhf-.
Interestingly, there appears to be little interaction between platinum and
axial water molecules. The second-order exchange rate of water molecules
in the plane is 4.5 x 10-
5
mol s -\ with MI*, 100 10 kJ mol-
l
and IlS*,
40 30 J mol-
l
K-
l
The first replacement of water by dmso has a similar
rate, and MI*, 90 1.5 kJ mol-
l
and IlS* 2 5 J mol-
1
K-
1
. The rate
constants for water replacement by CC Br-, 1-, SCN-, and C
2
H
4
are all
much larger than for the incoming groups H
2
0, dmso, and HgCl+. The
positive activation entropies for the H
2
0 exchange and dmso solvolysis,
and indications that steric hindrance in the activation process increases
reaction rate, point to a dissociative process operating in these cases. The
five fast-reacting ligands follow the conventional Ia mechanism. There
seems to be a gradual change in the substitution process of [Pt(OH
2
)4]2+
from Id to Ia as the entering group changes in the order H
2
0, dmso, Cl-,
Br-,r.
Inevitably, some studies on platinum(II) complexes are closely related
to analogous work on Pd(II). These include solvent effects on [Pt(Fo)L],(14)
analogous to 2. As with the palladium complexes, the mutual dependence
of reactivity effects on both entering and leaving ligands indicates a syn-
chronous mechar.ism, and the importance of steric effects is probably a
consequence of the rigidity of the chelate Fo. In general, nonspecific
solvation effects dominate the interchange reactions and the transfer Gibbs
free energy of solvation does not change on going to the transition state:
the only exceptions were due to initial state stabilization of the entering
ligands (by methanol) and transition state labilization for [FoPt(NH
3
)] in
strongly donating dmso and dmf. Initial state and transition state solvent
effects have also been reported(S) for the reactions of [ptC4]2- with water
and cyanide. Solvent effects on the transition states are somewhat larger
than on the initial state. These transfer data for the reaction of [PtC4f-
with 1,10-phenanthroline (phen) were unobtainable, since this reaction
proceeded by a dominant solvolytic loss of chloride.
The replacements of L (H
2
0 or dmso) from [Pt(dien)L];; by a variety
of nucleophiles all proceeded by direct bimolecular attack.(15) A nucleophi-
licity scale of Cl- < N
3
- < Br- < tu < SCN- < r < SeCN- < was
established. The S-bonded dmso was at least three orders of magni-
tude less labile than H
2
0, but the reactivity differences decreased with
the nucleophilicity of the entering groups. The 1T-bonding ligands
SeCN-, SCN-, and tu adopted anomalous positions on the nucleo-
philicity scale, presumably because of the effect of the +2 charge on the
substrate.
The increasing use of 195Pt nmr is emphasized by a study of the
substitution of coordinated water by acetamideY6) Equilibrium [equation
(5), L2 = (NH
3
h or en] was rapidly established, and the sensitivity of
[PtL
2
(OH
2
h]2+ + MeCONH
2
[PtL
2
(OH
2
)OCMeNH
2
]2+ + H
2
0
(5)
8 (Pt) to its coordination environment established that the acetamide was
o bonded rather than N bonded. These results, which are supported by
15N nmr measurements, could have implications to the mode of action of
Pt(lI) anticancer drugs. Also relevant to this field, the reaction (first order
in each reagent) of allyl alcohol with trans- [PtCh(NH
3
h] proceeds much
more quickly than with the cis isomer, predicted from relative trans
effectsY7) This has been developed into a simple spectrophotometric
method for estimating the amount of each isomer in solution.
The general increase in lability of palladium complexes over their
platinum analogs is illustrated by 31
p
nmr studies on cis-[MCI(PEt
3
hLf
(M = Pd or Pt; L = pyrazole or 3,5-dimethylpyrazole) in
dichloromethane. (18) The Pt complexes appear static, but the Pd compounds
reveal a rapidly (nmr time scale) averaged environment of the two cis-
triethylphosphine ligands. The rate-limiting step is pyrazole dissociation,
and Scheme 1 shows the proposed mechanism.
Scheme 1
solvent
--------'-
1ls0lvent
5.2 Substitution at Square-Planar Palladium(//) and Platinum(II) 111
5.2.3. Electrophilic Substitutions
The transfer of organic groups between palladium(I1) or platinum(II)
and mercury(I1) or thallium(III) are usually described as electrophilic substi-
tutions. In the transfer of aryl groups containing ortho -CH2NMe2 sub-
stituents from Hg(I1) or Tl(I1I) to palladium acetate, preliminary coordina-
tion of the nitrogen to palladium appears to be an important part of the
mechanism.(19) An intermediate structure (3) has been proposed prior to
Me2N"" /OAc

3
aryl transfer from Hg to Pd. The relationship of 3 to conventional intermedi-
ates from nucleophilic substitutions (see, e.g., structure 1) is obvious. There
is also a formal relationship between cyclic electrophilic substitution
(Scheme 2, path A) and cis-oxidative addition/reductive elimination
Scheme 2

X---M'
M-R

MX
+ +
M'-X

/
M'R
X-M-R
I
M'
sequences (Scheme 2, path B) and doubtless many transmetallation reac-
tions will proceed via a contribution from both extremes, where structure
4 best represents the transition state. A small displacement of the mercury-
.. R"

x
4
carbon bond in structures like 3 can produce just such Pd-Hg (M-M')
interactions. Cis-oxidative additions of HgCh to [PtMe2(bipy)] are already
known.(20) The reaction of [PtBr{(2,6-Me2NCH2)zC6H3}] and RHgCI
(R=N(p-tol)-N=NR' or N(ptol)-CH=NR'; R'=Me, Et, or Pr
i
) pro-
duces a five-coordinate complex with a platinum-mercury bond,(21) and
Scheme 3

+ CIHgN(R)YNR
NMe
2
<q5i
r
Me2
/
R
O
Pt-N
'I '\
N :y
Me2 /I
Cl-Hg-N
/ \
Br R
y Nor CR'
1

\
-NMe -NR
qS
l 21
o Pt--Hg-Cl
, \
NMe
2
Br
Scheme 3 depicts the likely reaction path, involving a transition state like
4. The reaction of mercury(II) acetate with [Pt(2-Me2NCH2C6H4)z] is
related, and produces compounds with mercury-platinum bonds. (22)
Equation (6) shows the most probable route, this time leading to a six-
coordinate product. There is evidence (electrochemical and uv /visible
AcO" /0
Hg(OAc)2
19 fMe
N N

( "'p( )
N 0
Hg(OAc).
--+
( '" /
(6)
)
/1'"
C/ "'c
c C
C c
N/
spectroscopy) that the metal-metal bonds are best described as platinum-to-
mercury donor bonds, (23) and such interactions can lead to oxidation of
5.3 Ring Opening and Closing Reactions 113
platinum, also.(24) We thus have clear evidence that the (normally empty)
axial sites of square-planar complexes can donate electron pairs from
normally filled orbitals, as well as accept donor ligands by nucleophilic
attack. Alongside the indications that both fa and fd reaction paths are
possible for nucleophilic ligand substitutions, the versatility of the square-
planar arrangement is quite remarkable.
An investigation into the substitution of the organic groups of
[PtMeAr(PMePh
2
h] and [PtMeAr(cod)] (cod = 1,5-cyclooctadiene) by
CI from HgCh reached the expected conclusion that aryl transfer conforms
more closely to an S
E
2 cyclic route (Scheme 2, path A), but methyl transfer
proceeds via an oxidative-addition/reductive-elimination sequence
(Scheme 2, path B).(25)
Finally, the formation of platinum(II) ylide complexes from halomethyl
derivatives is worthy of note [equation (7)].(26) Palladium analogs are more
[PtX(CH
2
X)(PR
3
h] + PR
3
-+ [PtX(CH
2
PR
3
)(PR
3
h]X (7)
reluctant to react in this way, and five-coordinate intermediates
[PtX(CH
2
X)(PR
3
h] are suspected. The transfer might then proceed
through transition states like S. The relationship to 4, involving contribu-
RaP Ra
I.p"
X-P(-'CH
I
' . 2
, .
RaP 'X'
5
tions from both electrophilic attack and oxidative-addition/reductive-elimi-
nation sequences,' is immediately apparent. Such internal transfer routes
have been postulated previously in rhodium cyclopentadienyl complex
rearrangements. (27)
5.3. Ring Opening and Closing Reactions
The reactions of palladium(II) aqua ions(28) and palladium(II)
chloride(29) with benzene-l,2-diol are first order in each reagent. The aqua
ion shows a combined [H+r
1
and [H+r
2
dependence, suggesting the
involvement of both Pd(OH);q and Pd(OHh(aq). The green 1: 1 chelate
complexes which result from these reactions are best considered as adducts
of Pd(O) and 0 -quinone, rather than Pd(II) and benzene diolate. The
reactions thus resemble those previously reported for benzene-l,4-diol
Scheme 4
[PdCI]+
-Cl-
-----"-

Pd(O)
\>"" #
1l
H

"'OJV
H
with Pd(II), or benzene-l,2-diol with Fe(III).(30) Scheme 4 illustrates some
of the important steps elucidated for the PdCh reaction.
Reactions of [PdCh(biL)] with 1,2-diaminoethane (en) in dmf yield
[Pden(biL)]Ch when biL is Ph
2
PC
2
H
4
PPh
2
(dppe), o-(Me2AshC6H4
(pdma), en, bipy, phen, or Ph
2
AsC
2
H
4
AsPh
2
as a first product, followed in
each case by the formation of [Pden2]Ch as final product. (31) The rate of
replacement of the first chloride in each case is strongly dependent on biL,
as would be expected, and values cover four orders of magnitude in the
order dppe > pdma > bipy > phen > en. When biL is PhSC
2
H4SPh,
however, this ligand is replaced before the chlorides, forming initially
[PdChen], and confirming the trans-effect order Cl- > PhSC
2
H
4
SPh.
Unlike the palladium analog, when the platinum complex [PtCh(bipy)] is
allowed to react with en or dithiooxamide, the bipy is inert towards
substitution. The reactivity of en is greater in dmf than in MeOH, and this
appears to be due to ligand-solvent interactions, probably hydrogen
bonding.
[Pden(OH
2
h]2+ reacts with the neutral molecule ethanolamine to form
a double chelate product. Potentiometric titrations showed that when
ethanolamine was replaced by amino acids, however, deprotonation was
necessary before the hydroxy group oxygen would coordinate.(32)
Acetylacetonates and complexes of related ligands are once again well
represented. Reactions of bis-13 -diketonate complexes of palladium(33-3S)
and platinum(35) with tertiary phosphines have been examined by
Kawaguchi and coworkers. Several reaction paths operated, depending on
the nature of the ligands, and featured five-coordinate species, monodentate
O-bonded or C-bonded diketonates, and compounds with uncoordinated
diketonate anions (Scheme 5).(35) Equilibrium constants for reaction 8,
Scheme S
0,
txo r..!.o
d l'L
H

-2L
"'----
D
'0

Jr-L

1l2L
measured from rates of the forward and back reactions, were reported as
1.38 x 10
3
in benzene, 4.35 x 10
3
in CH
2
Ch, and greater than 10
9
in
methanol. (33) This massive solvent effect is dependent on H bonding
between MeOH and the carbonyl oxygens.
[Pd(tfac)2] + P(o-tolh ---+
0 P(O-tOI}3
/-- " /
:,_ /Pd
'-
0
'oQCHa)=CHO(CF
a
)
CF
3
5.3.2. Platinum(II) Complexes
(8)
Recent work has allowed some interesting comparisons of ring opening
processes to be made between sulfoxide and sulfide chelates. These have
also been related to displacements of monodentate sulfoxides and sulfides.
Ring opening of meso - and racemic -1,2-{bis(phenylsulfinyl)ethane}di-
chloroplatinum(II) {6 and 7, respectively} by amines in dimethoxyethane
CI" ",P CI,.(:I
'pi 0 'pi Ph
'\.s/

Ph Ph Ph 0
6 7
showed no solvolytic contribution, which is characteristic of Pt(I1) reactions
in that solvent. (36) The racemic compound reacted about twice as fast with
pyridine as did the meso isomer, but this order was reversed when 2-
methylpyridine was used as incoming group. The difference arises from
steric interactions: the two sides of the racemic isomer 7 offer an entering
group the same hindrance, but the meso isomer 6 gives the nucleophile
two choices. The bond-making step was found to be the more important.
Interestingly, the rate constants for the second steps (displacement of the
bis(sulfoxide) to form cis-[PtChpY2]) were almost identical for the two
isomers.
Comparison with ring opening and displacement in
[PtCh(PhSC
2
H
4
SPh)] showed that both of the bis(sulfoxides) were more
reactive than the dithioether complex. (No isomer complexities were detec-
ted for this material, so either only one isomer existed in solution, or the
meso-racemic interconversions via sulfur inversions were fast compared to
ring opening.) The main difference between the two systems was that for
the chelating sulfoxide, ring opening was much faster than subsequent
ligand displacements, whereas the reverse was true for the disulfide.
The displacement of dmso from cis-[PtCh(dmsoh] by amines under
identical conditions revealed that the second-order rate constant, k
2
, was
also sensitive to the basicity of the entering nucleophile and to steric
hindrance.(37) The displacement of the first dmso was _10
2
easier than ring
opening of the bis(sulfoxide) chelates, and less sensitive to steric hindrance
than the less-congested meso -disulfoxide isomer. The bond-breaking step
from the five-coordinate intermediate appeared rate limiting, though it was
helped by an interaction (described as stereoelectronic to include lone-pair
repulsions) between the two cis sulfoxides which could not be accounted
for by independent trans and cis effects. The rapid ring opening of the
chelate bis(sulfoxides) probably reflected this. (36)
The kinetic cis effect of dmso was compared to that of Me
2
S in a study
of the displacement of X from [Pt(Me
2
S)enXr+ by various nucleophiles. (38)
Dmso had the greater effect. Further comparisons emerged from displace-
ment studies of Me2S from cis- and trans-[PtCh(Me
2
ShJ by amines.(39)
The bond-breaking transition state contributed much less to the overall
reactivity of the thioether and dithioether complexes than it did to the
reactivity of the corresponding sulfoxides.
A marked dependence on chelate ring size up to eight-member rings
emerged from a study of the reactions of [PtCh(dmso)]- with
NH
2
(CH
2
)nNH
2
and (controlled by pH variation).(40)
Followed spectrophotometrically, the first observed product when n is 2
or 3 was [PtCI(dmso)(NN)t, where NN acted as a chelate and ring closure
was fast compared to the entry of the amine to platinum. When n is 4,
however, the first observed product was [PtCh(dmso) (NN)], where NN
acted as a monodentate amine. Ring closure to a seven-member ring
competed with the entry of a second nucleophile. With n at 5 or 6, ring
closure made a negligible contribution to the slower, second step and the
conclusion was reached that the rate constant for formation of eight-
member rings was at least 40 times less than for seven-member rings.
Variations in the rate of the ring closure step of [PtCh(NH
3
)-
{NH2(CH2)nNH3}t (n = 2,3, or 4) have been examined at various pH
and temperatures. (41) Reactions followed the usual course, equation (9),
+ K
trans-[PtCh(NH
3
)(NNH)] trans-[PtCh(NH
3
)(NN)] + H+
+k
[PtCI(NH
3
)(NN)t + cr (9)
and indications were that the marked dependence on ring size arose from
differences in !:Jl* rather than llS*. In analogous organic ring closure
systems both contribute. A useful comparison is available from the kinetics
of ring closure of the dimethylamino analogs, [PtCh{Me2N(CH2)nNMe2H}]
(n is 2 or 3),(42) in basic media. Temperature variation studies gave llJl*,
43 3 and 57 2 kJ mol-
1
for n = 2 and 3, respectively, and llS*, -49 4
and -46 3 J K-
1
mol-
1
. These data were interpreted as indicating a
greater conformational stability for the five-member ring compared to the
six member. The methyl substituents caused a 50- to 100-fold rate enhance-
ment; an example of the Thorpe-Ingold or gem- dimethyl effect. When the
reactions were performed in acid media, a solvation step of the usual form
also contributes (Scheme 6).
A final example of ring closure of this type could prove to be one of
the most far reaching in its mechanistic implications. (43) Ring closure of
the P-N chelate 8 proceeds without retention of stereochemistry at Pt(II),
and appears to involve pseudorotation of the five-coordinate intermediate.
The product is the cis-(bis(chelate compound 9. Although the trans form
of 9 does isomerize to the cis version, that reaction is much slower than
its formation from 8. Moreover, the first-order conversion of 8 to 9 is not
affected by addition of trans-9 to the reaction, the trans isomer remaining
1l
Cl NN
"'./
Pt
/"'.
Cl Cl
\
Scheme 6
1l
".--...
Cl N N
"'./
Pt
/"'.
Cl OH
2
I
Cl N
"'./)
Pt
/"-
Cl N
unaffected during the ring closure of 8. Since associative pathways are
much more likely than dissociative ones in reactions of this type, geometry
change by pseudorotation of the five-coordinate intermediate seems the
most likely explanation for the products. This is the first such direct
observation of this phenomenon.
The immediate precursor in the preparation of 8 is the imido complex,
10. The convenient generation of 8 from this depends on the extremely
low trans effect of the imido group.(43)
10
5.4 Five-Coordinate Species 119
5.4; Five-Coordinate Species
The behavior of these species is fundamental to an understanding of
associative substitution mechanisms of four-coordinate complexes. Many
more such compounds have been examined, and it is not always clear
whether they should be regarded as intermediates or stable compounds in
their own right. Thus, for example, while there is good evidence that all
the reactions of palladium(II) and platinum(II) bis-{3 -diketonates with
tertiary phosphines proceed via association to five-coordinate species, some
cannot be observed at all, others can be detected in solution spectroscopi-
cally, and a few can even be isolated and crystallographically
examined. (33-35,44) Molecular structures of [Pd{CF
3
COCHCOCF
3
hP(o-
tolh] and [Pt{CF
3
COCHCOCF
3
}zPCY3] are both square pyramids with
apical (chelate) oxygens. lH and l3C nmr spectra in CD
2
Ch or CDCh
solutions show intramolecular fluxional behavior of the pseudorotation
type, and two such twist mechanisms were identified, resulting in site
exchange of different groups [equations (10) and (11)].(44)

0-/-0
(/ Pt /
o L
(10)
o
0
0-1"/0 (7 Pd!)o
Pd 0.. Pd: 0 I L (11)
"'.1\ : I
o L 0
L
The X-ray crystal structure of [Ph
3
PMeh[Pt(SnCh)S], on the other
hand, shows a trigonal bipyramidal ground state structure, with axial Pt-Sn
bonds shorter than the equatorial ones.(45) The anion is nonrigid in acetone
between 183 and 363 K C
95
pt and 119Sn nmr investigation), but coupling
is preserved, indicating again a nondissociative process, probably Berry
pseudorotation.
The stability, structure, and behavior of five-coordinate species is
greatly influenced by solvents, the ligands, and the nature of the metal. It
must be kept in mind that many of the studies reported in this section were
performed in solvents such as chloroform. In more polar methanol or water,
more commonly used in mechanistic studies of square-planar compounds,
the lifetime of any five-coordinate adducts may be too small to allow
detection, or for changes in geometry to occur. In a paper describing the
structure in CD
2
Ch solution and isolation of [PdX2(PMe3h], a comparison
was made of nickel, palladium, and platinum complexes of this type. (46)
The nickel compounds tended towards trigonal bipyramidal geometry, and
were fluxional by pseudorotation. The trigonal bipyramidal geometry was
less favored (though still often found) for palladium(lI), but quite rare for
platinum(II)' Intermolecular ligand scrambling became favorable compared
to intramolecular processes as the group was descended [equation (12)].
-8r- PM.,
[PdBr2(PMe3h] [PdBr(PMe3ht [PdBr(PMe3)4t (12)
A variety of trigonal bipyramidal Pt(II) complexes [PtClz(L)(biL)]
have been isolated and examined (L is 7J2-0 Iefin; biL is u-N,N'-a-diimine,
N,N'-disubstituted-l,2-diaminoethane, or 6-substituted-pyridine-2-
carbaldehyde imine).(47) The only intramolecular fluxional process detec-
ted eH, 13C, 15N, and 195pt vtnmr) in these molecules, however, was
rotation of the olefin (which occupies an in-plane equatorial site). The
expected diasterioisomers from use of a prochiral substituent on the amine
nitrogens were not found and an inversion at coordinated nitrogen via N-H
bond dissociation/recombination was responsible. The dependence of
geometry on the nature of the ligands involved was well illustrated when
the olefin of these diimine complexes was replaced by PBU3. The trigonal
bipyramid structure with apical chlorides, 11 (which was found even in
acetone or methanol), was converted to dimeric (12) or monomeric (13)
square-planar complexes. (48)
Bu'
;' /
Bu
3
P-Pt-N
,
CI ,
/N-,Pt-PBU3
But
CI
12
But
: /
/>-.. But
,
CI
13
Each of the axial halogen atoms, the equatorial olefin, and the nitrogen
chelate of 11 could be replaced with retention of the trigonal bipyramid
structure. (49) The rates of displacement were in the order halide < olefin <
N donor. The authors proposed a mechanism involving Pt-N bond dissoci-
ation leading to a square-planar intermediate related to 13 to account for
olefin or N -donor exchange. The incoming ligand could approach the square
via the vacant "axial" sites. To account for the (slower) halide replacement,
an ionic intermediate [PtCl(olefin)(biL)]Cl was suggested, though there
appears no precedent for a halide being lost without a geometry change
5.4 Five-Coordinate Species 121
to bring it to an equatorial site, and there is no evidence for such behavior
in these molecules.
A similar series of five-coordinate rhodium(I) molecules has been
examined.(SO) [RhCI(CO)(712-C2H4)(biL)] (biL = diimine) are trigonal
bipyramidal with axial Cl and CO in CDCh. The ethylene (which rotates
on the nmr time scale) is readily lost. The related compounds
[RhCl(COh(biL)] and [RhCl(PF
3
h(biL)] also contain trans-axial Cl and
CO or CI and PF
3
Intramolecular exchange of the CO sites is rapid,
however, suggesting an easier pseudorotation type of motion for these
complexes.
A study complementary to those described above involves nickel (II) ,
palladium(II), and platinum(II) complexes of meso - and racemic-o- pheny-
lene-bis(methylphenylarsine) and its phosphorus analog.(51) Both square-
planar [M(biLh]2+ and square-pyramidal [MX(biLht were examined. Of
the square-planar complexes, all those of platinum and palladium, and the
phosphine complexes of nickel, retained their identity in solution. The
nickel diarsine dication underwent an intermolecular ligand redistribution,
however, presumably via ligand displacement by solvent (CD
3
CN). The
five-coordinate species exhibited a range of behavior in solution. Rapid
site exchange of the chloride from one side of the square plane to the other
via an intermolecular route was found. Dimeric transition states with Cl-
bridging two metal atoms were favored by the authors. An intramolecular
isomerization of the chelate rings also occurred, and, in the palladium
diarsine complex, a redistribution process involving the chelate ligands also.
An interesting variation of four versus five coordination is afforded
by a series of di-2-pyridyl ketone complexes of Pd(II), Pt(II), and Au (III). (52)
The ligand coordinates in chelate fashion via the nitrogens, but protic
molecules HX (X = OH, OMe, or essentially solvate the complex by
converting the ketone to a diol form which can then also occupy the apical
coordination site. Structure 14 depicts such a hydrated gold(III) species.
q:'Cb,/fj} OH +
Au
c( 'NO
14
Rates of the reversible hydrolysis, and the stability of the hydrated species,
increased along the series Pt(1I) < Pd(II) < Au(III), parallel to the electron-
withdrawing properties of the metal cations, and their ability to form
square-pyramidal molecules.
122
5 Substitution Reactions-Coordination Nos. 4 and 5
Scheme 7
fasl
IrH(CO)L
3
IrH(CO)L
z
+ L IrH(CO)L + 2L
IrHY(CO)Lz + L IrHY(CO)L + 2L
L = PPh
3
, Y = H2 or PhC=CH
The fine balance of reaction pathways possible for some systems is
well illustrated by Scheme 7. (53) The iridium(I) atom can react with both
H2 (oxidative addition) or PhC=CH as a three-, four-, or five-coordinated
species, in equilibrium and in competition. In a similar vein, both the
four-coordinate and five-coordinate species from equilibrium (13)
[Ir(cod)phen]CI + X- [IrX(cod)phen] + Cl- (13)
(X- = r or SCN-) react with O
2
.(54) Kinetic studies at normal and elevated
pressures reveal that the five-coordinate species are much more reactive
to O
2
than the square-planar complexes: "end-on" O
2
addition is postu-
lated.
5.5. Isomerization of Square-Planar Complexes
Of late, this has been a particularly rich field of study, with some
recently recognized mechanisms being consolidated by further examples
of their operation, and yet new routes being discovered. The fluxional
nature of some five-coordinate intermediates and their possible role in
isomerization mechanisms is particularly notable.
Nuclear magnetic resonance spectroscopy enabled the two methyl
groups of the acetylacetonate complex 15 to be distinguished in CDCh
solution.
15
Donors such as pyridine or PPh
3
catalyzed a rapid isomerization which
resulted in nmr equivalence for the methyl groups. Reactions were first
5.5 Isomerization of Square-Planar Complexes 123
order in both substrates, and activation parameters indicated associative
control. (55) A variety of donor solvents promoted the isomerization also,
providing clear evidence for solvent catalysis of such processes. The
efficiency of the solvents decreased in the order HMPA > dmso > MeOH >
MeCN > dmf > MeN0
2
> Me2CO > thf. The mechanism proposed
(Scheme 8) essentially extends that shown in Scheme 5.
Scheme 8
1l
The sulfur-bonded complexes (16) (M = Ni, Pd, or Pt) convert from
the trans form, in which they crystallize, to a 1: 1 cis-trans mixture in
solution (note that in this case the geometry refers to substituent positions
above and below the coordination plane).(56) In organic solvents, the rate
of isomerization (followed by nmr spectroscopy) is M = Ni Pd > Pt. The
palladium compound in benzene has a negative entropy of activation. In
CS
2
the isomerizations proceed ten times faster. A solvent-assisted M-S
bond-breaking process with the dissociative step being rate controlling fits
the data obtained. The fact that even nonpolar benzene assists such a process
provides yet further evidence of the importance of solvation in reaction
sequences.
Autocatalysis as an isomerization mechanism finds support in a number
of recent publications. Tetrahydrofuran(thf) has no detectable catalytic
effect on the isomerization of complex 15, but a slow geometry change in
that solvent does, nevertheless, take place.(55) It seems likely that the
catalyst is PPh
3
, displaced from 15 according to equation (14). The induction
period in the (apparently non catalyzed) isomerizations of some platinum
complexes [PtX
2
L
2
] (L = R
3
P)(57) has been attributed to the operation of
reaction (15). When L reaches a value where reaction (16) becomes faster
than (15), the observed pseudo-first-order characteristics for the isomeriz-
ation would result.
2[PtX
2
L
2
] [PtzX
4
L
2
] + 2L (15)
cis- or trans-[PtX
2
L
2
] + L trans- or cis-[PtX
2
L
2
] + L (16)
One of the most interesting but controversial mechanisms for isomeriz-
ation proposed in recent years is the three-coordinate route: spontaneous
ligand loss to form a T-shaped intermediate which changes geometry. In
the period under review more such species have been proposed and new
ideas on the geometry change step have helped to explain previously difficult
areas of interpretation.
Equation (17) depicts the formation of a species claimed to be three-
coordinate in solution, though it may well be solvated (CH
2
Clz).(58) The
cis -[PtClz( CH
2
PPh
3
)PPh
3
] + AICh ---+ [PtCI( CH
2
PPh
3
)PPh
3
][ AICI4] (17)
cation reversibly adds acetonitrile but stronger donors such as PPh3 or
SMe2 coordinate more permanently. The geometry of the four-coordinate
adducts so formed can vary, and this could reflect a fluxional three-
coordinate complex. The kinetic products can also change geometry by
unknown routes (Scheme 9).
More examples of f3- and ')I-eliminations from organoplatinum com-
plexes which proceed by spontaneous ligand loss to form three-coordinate
intermediates have been reported. (59) Loss of Et3P from cis -[PtEtz(PEt3h]
is followed by f3 -hydrogen transfer, but deuteration studies indicate that
the two ethyl groups of the T -shaped intermediate are equally likely to
Scheme 9
undergo the elimination process. This suggests a fluxional process of the
type illustrated by equation (18) must operate faster than the (3 -elimination
(18)
step.(S9a) Such geometry changes are, of course, central to isomerizations
via T -shaped three-coordinate intermediates. A crystal structure determi-
nation on cis-[Pt(CH2CMe3h(PEhh] indicates that loss of PEh (which
precedes y-H migration) may considerably relieve steric strain.(S9) This
may be an important factor in related ligand-loss processes.
A useful combination of theoretical and practical work sheds some
light on how the central geometry change at the T -shaped species may
come about in some cases. Extended Hiickel calculations indicate that
there is a considerable barrier to isomerization of isolated T -shaped trans-
[PdR2L] to the cis isomer, though when the R groups are poor donors,
cis-trans isomerizations will be more facile than reductive eliminations. (60)
Thermolysis studies on trans -[PdR
2
(PR' 3h] in acetone-d
6
indicate that
isomerization to the cis isomer precedes decomposition by reductive elimi-
nation. (61) Both processes involve elimination of PR;, and are suppressed
in the presence of excess ligand. The equilibrium trans/cis ratio depends
more on the electronic nature of PR; than its bulk, more phenyl substituents
favoring cis geometry. Deuterated methyl derivatives revealed that the
methyl groups are scrambled during the isomerization, clearly indicating
intermolecular steps. Equations (19)-(21) account for all the observations,
including the rate data.
(19)
(20)
[
L" ] fast. [ ]
/ Pd " + L ---+ ClS- PdRR'L2
R R'
(21)
Equation (20) is the R-scrambling step, and probably proceeds by
alkyl-bridged intermediates like 17. Initially, the isomerization is slow,
L.. ,R. R'
'. --- .1
Pd Pd-L
rf "R'/ L
17
since the amount of cis-[PdR
2
L
2
] present to take part in reaction (20) is
extremely small. Initial formation of the cis-[PdR2L2] catalyst could come
about via a direct isomerization of the three-coordinate [PdR
2
L], discussed
above, but increased concentration of trans -[PdR
2
L
2
] accelerates the pro-
cess somewhat so a process like equation (22), analogous to but slower
than (20), could operate.
(22)
Bridging organic groups are often featured as a mechanism of transfer
in this area of the periodic table. Equations (23) and (24)(62) (L = PPh
3
)
L
I .' "
I-Au AU-L (23)
Je'\.c/
D3
cis-[AuMe(CD3)IL] + [AuMeL]
cis-[AuMe
2
IL] + [AuMeL] (24)
->- [AuMeaL] + [AuIL]
feature bridging methyl groups between Au (III) and Au(I), and such
intermediates are common in organomercury chemistry. This is the first
time such an intermolecular process has been recognized as an isomerization
route, however.
Yamamoto and co-workers(61) also described a trans to cis isomeriz-
ation of [PdMe2L2J catalyzed by methyl-lithium. This, too, involved methyl
group exchange, but is of the more conventional associative reaction type.
The route may be consecutive displacement (shown in Scheme 10), though
pseudorotation of the five-coordinate sEecies cannot be ruled out.
Coincidentally, Gillie and Stille( 3) also reported isomerization of
[PdMe2L2] catalyzed by donor solvents (thf or dmf) or free L. While the
Scheme 10
L ]
L Li Me-fd-Me
CD3
mechanism is presumably related to the associative path of the MeLi-
catalyzed reaction (consecutive displacement or pseudorotation), no
catalytic effect of free phosphine was found in that work:(61) rather, its
presence suppressed the alternative dissociative pathway. It may well be
that once again a variety of reaction pathways of similar activation energy
is available to complexes of this nature.
Studies on photochemical isomerizations of bisphosphinepalladium
dihalides indicate the operation of non dissociative mechanisms. The pres-
ence in solution of excess halide or phosphine had no effect on the quantum
yields, (64) and no phosphine exchange accompanied the isomerizations. (65)
Excitation of a phosphine -+ palladium charge transfer band was respon-
sible for the change, and the rates followed the same sequence as ligand
lability, so a mechanism involving a distortion from planar to tetrahedral
geometry seems likely. (64) Finally, cis -[Pt(SRhL
2
] (R are alkyls; L are
tertiary phosphines) isomerize to the trans materials when in contact with
oxygen!(66) Although the mechanism is unknown, free-radical intermediates
are suspected. Sensitivity to air is uncommon among platinum complexes
of such ligands, but this inertness of air obviously cannot be assumed in
studies of this sort.
5.6. Gold(lII) Square-Planar Complexes
Recent studies include a number of substitution reactions accompanied
by or preceding reductions or ligand reactions. Stopped-flow spectro-
photometry on the reaction of thiocyanate with tetrachloroaurate(III) or
tetrabromoaurate(III) revealed two kinetically distinct reaction stages. (67)
The first stages were rapid stepwise substitutions to [AuX(SCNhr
[equation (25), n = 0-3]. The solvent (H
2
0) path was negligible, and no
evidence for persistent five-coordinate intermediates was found. The sub-
sequent, slower, reaction was a reduction to Au (I) , involving an inter-
molecular reductive elimination. Equation (26) shows the overall process.
3[AuX
4
r + 7SCN- + 4H
2
0 -+
3[Au(SCNhr + HS0
4
+ HCN + 12X- + 6H+ (26)
A related study followed the reduction of [AuC14r and [AuBr4r by
iodide. (68) In these cases reduction was faster than ligand substitution, so
there was no initial replacement of Cl- or Br - by r prior to reductive
elimination.
5.7 Miscellaneous
129
The gold(III)-promoted hydrolysis of thioesters has a ligand substitu-
tion as its first step [equation (27)].(69)
[AuC1
4
r + ArCOSEt [AuChS(Et)COAr]
-CI 2H
2
0
(27)
5.7. Miscellaneous
5.7.1. Bridged Complexes
Addition of PMe2Ph (L) to chloroform solutions of [Pt
2
Clz(1L -ClhL
2
]
produced the ions [ptCIL3r and [ptChLr as major products, even at low
temperature and with fast mixing. (70) It appears that asymmetric bridge
cleavage took place with both entering nucleophiles attacking the same
platinum atom [equation (28)]. Previous examples of such asymmetric
cleavage had been confined to chelating nucleophiles, or to systems where
the asymmetry could arise from secondary t:earrangements of the initial
cleavage products. The nature of the nucleophiles in equation (28) is
important. Some other phosphines, both as entering or resident ligands,
did not produce the same effect.
[PtzC14 LzJ l ':. [PtClL,r + [PtCJ,Lr
L Cl J
(28)
18
Although the presence of singly bridged binuclear complexes like
intermediate 18 of equation (28) has been clearly shown kinetically in
previous studies (e.g., see Ref. 6), there are few complexes of this type
known. Species 19, isolated from the reaction of [Pt2CI4(PEhh] with
NaS2CNMe2, provides another rare example.(71)
The normally rapid bridge cleavage reactions of halogen-bridged bi-
nuclear platinum complexes was found to be considerably slower with very
bulky terminal groups like P(cyclo -C
6
Hllh, (PCY3), and this afforded a
method of synthesis from mononuclear compounds [equation (29)]. (72) With
less bulky nucleophiles, the dimer is cleaved too rapidly and trans-[PtClzL
2
]
is preferentially produced.
2K[PtCh(C2H4)] + 2PCY3 ..... trans -[Pt2Clz(1-' -Clh(PCY3h] (29)
Bridge cleavage reactions of palladium(1I) complexes are more sensi-
tive to the nature of the substituents. Equilibrium (30) (L = PPh
3
),
Y
2 V:p/ 2L + \;C\;--o (30)
Y L/ "Cl 6-:(
measured in dmso or MeCN, is very sensitive to the benzyl substituent, Y.
Electron-withdrawing CN in 0, m, or p position shifts the equilibrium to
the left. (73)
The formation of halide-bridged complexes between square-planar
and octahedral complexes is also well known [e.g., equation (31)].(74) Such
[IrCI4(PMe2Phhr + trans-[PdClz(AsMe3hJ -AsMe"
PMe
2
Ph
CI"" I /Cl
Ir Pd
CI/ I "CI/
(31 )
PMe
2
Ph
species probably act as intermediates in the oxidation of square-planar
iridium(I) complexes to octahedral iridium(III) by transfer of two CI from
Rh(III) or Pt(IV) compounds [equation (32)]. (75)
[RhCh(CO)(PR
3
hJ + trans-[IrCl(CO)(PR3hJ .....
trans-[RhCl(CO)(PR3hJ + [IrCb(CO)(PR3hJ (32)
Two interesting cleavage processes involve the so-called "A-frame"
complexes of palladium with dppm. The slow step of equation (33) probably
5.7 Miscellaneous

fast
slow

131
2[PdX
2
(dppm)
(33)
involves the formation of halide bridges as in structure 20, prior to releasing
a phosphorus of dppm. (76) Treatment of the trihydride complex 21 by
nucleophiles, L, results in H2 elimination [equation (34)].(77) It is probable
that bridge cleavage to species like 22 precedes the elimination.
+
+L
(34)
5. 7.2. Other Reactions
Oxidative addition of methyl iodide to [Ir(cod)(phen)t proceeds by
two competing routes, both involving five-coordinate intermediates. (78) The
preferred pathway is coordination of 1- to form [IrI(cod)(phen)], hence
the reaction is catalyzed by free r. The other route is electrophilic attack
of CH
3
The comparison with oxygen oxidation, which also preferentially
proceeds through this five-coordinate iodide adduct, (54) is interesting.
The reactions of equation (35) were examined by
17
0 nmr spectroscopy
and T-jump methods to explore the relationship between square-planar,
five-coordinate, and octahedral nickel(II) complexes. (79) The k Ii L I step
was considered rate determining, and values of L2 and k 1 of (1.05 0.09) x
10
7
S-I and (5.8 0.03) x 10-
3
mol-
1
dm-
1
s-\ respectively, were reported
at 25C. The overall equilibrium, K I between square-planar and octahedral
species was (490 20) x 10
4
, and MfO for the change was put at 15
0.3kJ mol-I.
Finally, the tetradentate macrocycle (23), related to 12-ane-N
4
above,
forms a square-planar complex with Cu
2
+, but the smaller Ni2+ does not
riO
NH HN
OJ:
NH
HN)

23
fit so well. (80) The strained geometry of the copper complex facilitates
conversion of the d
9
copper(1I) to d
8
Cu
3
+. The EO value of 0.42 V is in
the range reported for peptide complexes.
Chapter 6
and Above: Chromium
6.1. Introduction
This review covers the period between the end of the previous report(l)
and literature available up to July 1982. Two reviews have appeared, one
dealing with chromium coordination chemistry,(2) and a second concerning
attempts to distinguish between D and Id mechanisms. (3)
6.2. Aquation and Solvolysis of Chromium(III) Complexes
6.2.1. Unidentate Leaving Groups
6.2.1.1. Aquo Complexes
The [(H
2
0)sCrH]2+ ion can be prepared by uv flash photolysis of
aqueous chromium(II) perchlorate.(4) Previously it was made by pulse
radiolysis.(S) The ion is characterized by a uv peak at 385 nm, and is
shortlived owing to its rapid reaction with H30+ ion [equation (1)]. At an
[(H
2
0)sCrH]2+ + H
3
0+ ---. [Cr(H
2
0)6]3+ + H2 (1)
133
134 6. Substitution Reactions-Coordination Nos. 6 and Above: Chromium
ionic strength, [ = 0.2, reaction (1) is characterized by a rate constant at
299.2 K of (1.0 0.1) x 10
4
dm
3
mol-
1
s-\ and activation parameters:
MIt = 26.4 0.9 kJ mol-\ !!:.st = -79.9 2.9 J K-
1
mol-
1
. The +2
charge is confirmed from a plot of In(k) versus 0.509[1/2/(1 + [1/2) which
has a slope close to the theoretical value of 2ZAZ B (ZA = +2, ZB = + 1).
The [CrHf+ ion reacts with H+ much more readily than the analogous
[CrMe]2+ ion (by a factor of 2 x 10
6
), and there is a marked isotope effect
for the protonolysis of [CrHf+ in H30+ compared with [CrDf+ in D
3
0+
(kH/kD = 4.8). For acidolysis of [CrMe]2+ in H30+ or D30+, kH/kD = 6.3.
A mechanism in which O-H bond cleavage is more important than either
Cr-H or Cr-C bond cleavage is proposed to account for these results.
Several papers have appeared dealing with reactions of [(H
2
0)sCrR]2+
ions (R = alkyl or hydroxyalkyl), including reactions with Fe
3
+, Cu
2
+, or
Hg2+ ions,(6) homolysis or hydrolysis,(7.8) and trans substitution.(9) For the
reactions of a-hydroxyalkyl complexes [(H
2
0hCrCR'(OH)Rf+ (R = Me,
Et, or 2-Pr) with Fe
3
+ and Cu
2
+, the immediate products are [Cr(H
2
0)6]2+,
the reduced oxidant (Fe2+ or Cu +) and the corresponding aldehyde or
ketone. The following rate law applies (M = Fe3+ or Cu2+):
-d[CrCR'(OH)R
2
+]/dt = (k1 + k
2
[H+r
1
)[CrCR'(OH)R
2
+][M] (2)
The k2 term is dominant with k2 varying with Rand R' as shown in Table
6.1. For the [(H20)CrCMe2(OH)]2+ ion homolysis of the Cr-C bond is
involved, whereas for the other ions a mechanism involving attack by the
oxidant at the alcoholic OH group is favored:
k
M
n
+ + [(H
2
0)sCrC(RR')OH]2+ k 3. [(H
2
0)sCrC(RR')OMr+1)+ + H+
(3)
[(H
2
0)sCrC(RR')OM](n+1)+ Cr(aq)2+ + Cu(aqt + RR'CO (4)
With this scheme the electron transfer step is rate limiting and k2 =
k3k4/ L
3
. An alternative scheme for Fe
3
+ involving a rate-limiting ligand
substitution process on [Fe(OH)]2+ could not be ruled out. Replacement
Table 6.1. Variation of k2 Values with Alkyl Groups for Rate Law
(2). (Reactions Studied at 25C in 1 mol dm -3 Parent Alcohol-Water
Mixtures; 1= 1.0; Data from Ref 6)
k
2
/s-
1
(Cu
2
+)
k
2
/s-
1
(Fe
3
+)
0.251
0.496
-CH(Me)OH
1.46
0.481
0.574
1.90
6.2 Aquation and Solvolysis of Chromium(IlI) Complexes 135
of the alkoxy OH group by OR groups leads to no reaction with Cu
2
+,
and the rate of reaction with Fe3+ is greatly reduced (102k
2
/s -1 = 1.27 and
4.0 for [CrCH
2
0Mef+ and [CrCH(Me)OEtf+ in 1 mol dm -3 methanol).
For the reactions of [CrCH
2
0Rf+ ions (R = H or Me) with Hg
2
+, an
acid-independent electrophilic SE2 substitution occurs, and the immediate
products are [Cr(H
2
0)6]3+ and [HgCH
2
0Rr. The organomercurials sub-
sequently decompose rapidly to give CH
2
0 (R = Me or H) and
MeOH (R = Me). In contrast the [CrCMe20H]2+ ion undergoes a
I f
. . h H 2+ . H + d C 2+
one-e ectron trans er reaction WIt g to gIve g2 an r,
with k/(dm
3
mol-
1
S-l) = 166 + 467/[H+] at 298.2 K, whereas
[CrCH(Me)OEt]2+ is involved in a two-electron transfer to give Hg(O) and
Cr
3
+ with k/(dm
3
mol-
1
S-l) = 0.535/[H+]' The [CrCH(Me)OHf+ ion also
reacts by both routes, -15% by the one-electron pathway and -85% by
the two-electron pathway.(6)
[CrCHMe2f+ + O
2
+ H+ -+ [Cr(H
2
0)6]3+ + Me
2
CO (5)
The [(H20)5CrCHMe2f+ ion reacts with O
2
as shown in equation (5).
Smaller amounts of [HCr04r, [Cr2(OH)z]4+, and Me
2
CHOH are also
formed, and the unusual rate law =
(k = 0.49 0.06 dm
3/2
mol-
1/2
s -1 at I = 1.0 and 298.2 K) is observed.
The reaction is independent of [0
2
] and [H+], and a chain mechanism
involving SH1 homolysis of the Cr-C bond (10
4
k = 1.78 0.11 S-l) is
proposed. Of two possibilities, the following mechanism is favored with
k = (kd2k4)1/2k3 as in Scheme 1. Very low concentrations of Fe
2
+ or high
Scheme 1
[CrCHMe212+ Cr
2
+ + 'CHMe2
'CHMe2 + O
2
Me2CHOO'
Me2CHOO' + [CrCHMe212+ [CrOOCHMe212+ + 'CHMe2
2Me2CHOO' Me2CHOH + O
2
+ Me2CO
[Cu
2
+] inhibit the reaction markedly by competing for Me2CHOO' or
[CrOO'f+:
Me2CHOO' + 3Fe
2
+ + 3H+ -+ Me
2
CHOH + 3Fe
3
+ + H
2
0
[CrOO']2+ + 3Fe
2
+ + 4H+ -+ Cr
3
+ + 3Fe
3
+ + 2H
2
0
For the Cu
2
+ inhibition, kobs = k
Cu
[02][CU
2
+rt. with Me2CH(R) and
Me2CHOO(ROO') acting as chain-carrying intermediates.(7) Acid hydroly-
sis in the absence of O
2
gives Cr(aq)3+ and C
3
Hs in a first-order process
with 104k = 1.05 0.02 s -1 at I = 1.0 and 298.2 K. Data have been repor-
ted for the acid hydrolysis and homolysis of a large number of (a-
hydroxyalkyl)- and (a-alkoxyalkyl)-pentaaquo chromium(III) ions.(S) The
acid hydrolyses are electrophilic processes involving heterolytic Cr-C bond
cleavage. Both [H+]-dependent and [H+]-independent pathways are obser-
ved as in equation (6). The transition state for the [H+]-dependent pathway
k = kl + k
2
[H+] (6)
is pictured in structure 1. The [H+]-independent pathway is similar, with
H
2
0 rather than H30+ acting as the attacking electrophile. It is quite likely
that a coordinate (more acidic) water molecule is involved in the k 1 pathway
(2).
[
1
2
+
I 1 2
(H
2
0l
s
(r---((R R lOR
1
Values of kl and k2 and associated activation parameters are collected
in Table 6.2 together with the homolysis rates. The values of kl for the
"internal" pathway are not very different for the several species studied,
whereas values of k2 for the H30+ pathway vary considerably with changes
in the alkyl substituents, particularly those on the a-carbon atom. Interest-
ingly, the organochromium cation derived from diisopropyl ether,
[(H20)SCrC(Me)OCHMe2]2+, rearranges rapidly in acid solution to give
the isomer [(H20)sCrCMe20Hf+.
The homolysis rates (Table 6.2) are associated with an SHl mechanism,
and were obtained using oxidizing scavenger metal ions. The enthalpies of
activation are large (20-37 kcal mol-I) as expected for such a process.
Values of the very small equilibrium constants, K
H
, for equilibrium (7)
[(H
2
0)sCrC(R'R
2
)ORf+ + H
2
0 [Cr(H
2
0)6f+ + 'C(R'R
2
)OR (7)
were estimated and a plot of log kH (S-I) versus log KH found to be linear
with a slope of 0.93. Making reasonable assumptions, values of MIt may
be approximated to MI H, the enthalpies of homolysis of the Cr-C bonds. (S)
The trans effect of alkyl, hydroxy-alkyl, and alkoxy-alkyl groups in
[(H
2
0)sCrRf+ ions (R = CH
2
0H, CH
2
0Me, CH
2
CN, or CHMe2) have
been established from studies of the 1 : 1 anation reactions with thiocyanate
ion.(9) The data are consistent with either a D or an Id mechanism:
T
a
b
l
e

6
.
2
.

R
a
t
e

C
o
n
s
t
a
n
t
s

a
n
d

A
c
t
i
v
a
t
i
o
n

P
a
r
a
m
e
t
e
r
s

f
o
r

t
h
e

A
c
i
d

H
y
d
r
o
l
y
s
i
s

a
n
d

H
o
m
o
l
y
s
i
s

o
f

[
(
H
z
O
)
s
C
r
C
(
R

l
R

z
)
O
R
F
+

I
o
n
s

a
t

2
9
8
.
2

K

a
n
d

I

=

0

(
D
a
t
a

f
r
o
m

R
e
f
.

8
)

1
0
5
k
t
!

f
i
l
i
i
!

!
:
:
.
S
t
!

1
0
5
k
2
/

I
i
l
i
V

!
:
:
.
s
t
/

k
H
/

R

R
l

R
2

s
-
1

k
c
a
l

m
o
l
-
1

c
a
l

K
-
1

m
o
l
-
1

d
m
3

m
o
l
-
1

S
-
1

k
c
a
l
m
o
l
-
1

c
a
l

K
-
1

m
o
l
-
1

S
-
1

H

H

H

6
6

4
6
.
5

3
.
7

x

1
0
-
5

H

H

M
e

1
9
0

1
2
2

8
.
5

x

1
0
-
4

H

H

E
t

3
1
7

2
1
4

1
.
0
1

x

1
0
-
3

H

M
e

M
e

3
3
0

1
7
.
1

-
1
1

4
7
0

1
9
.
4

-
5

0
.
1
2
7

H

M
e

E
t

8
0
0

4
6
,
9
0
0

1
5
.
6

-
8

0
.
9
2

H

E
t

E
t

3
0
0
0

8
5
,
8
0
0

1
2
.
1

-
1
8
.
3

8
.
3
9

H

M
e

P
r
i

3
5
0
0

1
9
.
7

0
.
5

3
0
,
0
0
0

1
5
.
4

-
1
0

2
1
.
6

H

M
e

B
u
'

-
3
0
0

M
e

H

H

<
0
.
1

<
0
.
1

<
1
0
-
6

E
t

H

M
e

s
5

x

1
0
-
2

3
.
8

2
.
0

x

1
0
-
3

P
r
i

M
e

M
e

5
.
7
7

H

H

C
F
3

<
0
.
1

<
0
.
1

<
3

x

1
0
-
5

!
J
\

.
.
c
:
.

I
:
:

I
:
l

;
:

I
:
l

;
:

s
:
:
.
.
.
.

e
-
o

1
;
;
.

:
i

;
:
;
.

:
i

-
;
:
:
:
:
,

:
:
:
:
:

'
-
'

g

.
.
.
.
.

.
.
.
.
.
.
.

Table 6.3. Comparison of the Rates of Loss of the trans- Water Molecule from
[Cr(HzO)sXF+ Ions at 298.2 K and I = 1.0
CH
2
0H CH
2
0Me
;;;:1520 20.6
CHCl
2
0.0462
CHMe2
3.16
I
2.7 x 10-
4
Cl
2.4 x 10-
5
NCS
1.5 X 10-
5
kobs = (A[SCN-] + B)/(1 + C[SCN-]) (A, B, and C are constants). Values
of AI C approximate to rate constants for H
2
0 exchange, and these data
are compared with previously determined results for [(H
2
0)sCrX]2+ ions
(X = CH
2
CI, CHCh, I, CI, or NCS) in Table 6.3. The data correlate with
the electron-donating ability of the R groups as measured by the Hammett
substituent constants, (1'/. Values of the equilibrium constants fall in the
range 3.5 (R = CH
2
CN) to 19.1 (R = CHMe2).
The kinetics of aquation of [(H20)sCr02CCCh]2+ ion have been
measured between 35 and 55C at 1= 1.0 and with [H+] in the range 0.01
and 1.0 mol dm-
3
The pseudo-first-order rate constant, k, varies with [H+]
(8)
as shown in equation (8) (a-d are constants); at 45C, 10
7
a/mol dm -3 s -1 =
1.41 0.03, 10
5
bls-
1
= 1.66 0.02, 10
5
cldm
3
mol-
1
S-1 = 7.0 0.8, and
dldm
3
mol-
1
= 2.3 0.3. The authors reject the "normal" mechanism
involving loss of a proton from a coordinated H
2
0 molecule and protonation
of the carboxylate group [reactions (9) and (10); R = CCh], in favor of
K
[(H
2
0)sCr02CR]2+ + H+ [(H
2
0)sCrOHCOR]3+ (10)
attack at the carbonyl group [reactions (11)-(13)] in addition to loss of the
trichloracetate from the conjugate base [reaction (14)]. With this mechan-
ism [reactions (11)-(14)] the parameters of equation (8) are assigned as
[(H
2
0)sCr02CR]2+ + H
2
0 [(H
2
0hCrOCCOHhR]2+ (11)
k2
[(H20hCrOCCOHhR]2+ + H
2
0 products
[(H
2
0MHO)Cr02CRt products
(13)
(14)
6.2 Aquation and Solvolysis of Chromium(lII) Complexes 139
Table 6.4. Activation Parameters Associated with the Parameters in Equation (8)
(Data from Ref 10)
Parameter
All" jkJ mol-
1
AS'jJ K-
1
mol-
1
a
136 3
49 10
b
93 6
-44 18
c
87 3
-58 8
d
-1121
-28 65
follows: a = kJ(a, b = (k4kJ(a + klks)/(k2 + ks), c = k3kS/(k2 + k
s
), and
d = k
4
/(k
2
+ k
s
). The values of !::J[* for the H+ -assisted and acid-indepen-
dent pathways are notably lower than those found for the inverse hydrogen
ion pathway, indicating Cr-O fission for the latter and C-O fission for the
two former pathways.(10) The data are collected in Table 6.4.
The rate loss of CN- ion from [Cr(CNh(H20hNO] has been found
to be catalyzed by H+ (normal H+ catalysis) and buffer ions RCO
z
(R = Me
or a-chloro-derivative), whereas for [ON(H
2
0)4CrNCHg]3+ ion only a
dependence on [RCO
z
] ion is observed. The buffer ions catalyze these
reactions by ion pairing. (11)
Rates of water exchange in [Cr(NH
3
)6-AH
2
0)xJ
3
+ ions are discussed
in the next section.
6.2.1.2. Ammine and Amine Complexes
A recent study of the rate of water exchange with mer-
[Cr(NH
3
h(OH
2
h]3+ and [Cr(NH
3
)(OH
2
)s]3+ ions completes the picture
with respect to exchange rates for all species of the type
[Cr(NH
3
)6-x (H
2
0)x]3+. The latest set of activation parameters are compared
with some previous results in Table 6.5. Water molecules in trans positions
to NH3 are significantly more labile than those in trans positions to H
2
0,
and the rates are decelerated by the introduction of cis-H
2
0 molecules,
although not in a regular fashion. The data are consistent with an Ia
mechanism in which the major cause of the cis effect is the ligand-ligand
interactions between the four cis ligands and the incoming and outgoing
H
2
0 molecules in a symmetric seven coordinate transition state. The
reactions proceed with retention of configuration. (12)
The [Cr(NH
3
)sS]3+, trans-[ Cr(NH
3
MS)Cl]2+, and trans-[ Cr(NH
3
)4S2]3+
ions (S = DMF or DMSO) have been prepared, and the rates of hydrolysis
of [Cr(NH
3
)s(DMF)]3+ and trans-[Cr(NH
3
MDMF)Clf+ ions reported.(13)
For the former ion only loss of DMF is involved (10sk = 1.07 s-t, !::J[* =
21.5 0.3 kcal mol-t, !1S* = -9.3 0.9 cal K-
1
mol-I), whereas for
trans- [Cr(NH
3
MDMF)Clf+ simultaneous loss of Cl- and DMF occurs with
retention of configuration; for the loss of Cl-, 106k = 1.87 S-I, !::J[* =
T
a
b
l
e

6
.
5
.

R
a
t
e
s

a
n
d

A
c
t
i
v
a
t
i
o
n

P
a
r
a
m
e
t
e
r
s

a
t

2
9
8
.
2

K

a
n
d

1
=

1
.
0

f
o
r

W
a
t
e
r

E
x
c
h
a
n
g
e

w
i
t
h

[
C
r
(
N
H
3
)
6
_
.
(
O
H
2
)
x
j
3
+

I
o
n
s

(
0

<

x

5
5
)

(
D
a
t
a

f
r
o
m

R
e
f
.

1
2
)

H
2
0

i
n

t
r
a
n
s

p
o
s
i
t
i
o
n

t
o

N
H
3

H
2
0

i
n

t
r
a
n
s

p
o
s
i
t
i
o
n

t
o

H
2
O

c
i
s

l
i
g
a
n
d
s

1
0
5
k
/
s
-
1

/
:
l
l
{
*

/
k
J

m
o
l
-
1

.
i
s
*

/
J

K
-
1

m
o
l
-
1

1
0
5
k
/
s
-
1

/
:
l
l
{
*

/
k
J

m
o
l
-
1

.
i
s
*
/
J

K
-
1

m
o
l
-
1

(
N
H
3
)
4

5
.
7
5

9
9
.
1

1
.
4

+
7
5

1
.
1
7

9
8
.
5

2
.
1

-
9
7

(
N
H
3
h
(
O
H
2
)

5
.
9
2

9
5
.
1

1
.
9

-
7
6

1
.
2
3

c
i
s
-
(
N
H
3
h
(
O
H
2
h

5
.
7
8

9
5
.
1

1
.
3

-
7
5

1
.
0
2

1
0
5

4

+
1
3

1
4

t
r
a
n
s
-
(
N
H
3
h
(
O
H
2
h

7
.
6

0
.
9
9
7

9
7
.
0

1
.
1

-
1
5

4

(
N
H
3
)
(
O
H
2
h

4
.
9

1
0
1

3

1
1

9

0
.
4
4
9

(
O
H
2
)
4

2
.
8

0
.
2
4
6

1
0
9
.
6

1
.
3
0

1
6

5

.
.
.
.
.

-
t
.
.

0
\

:
:
:
-
.

l
2
'

5
-
;
:
c

.
.
.

s
:
:
.

C
'>

g
-
T

g

c

a
.

s

s
:
:
.

5
-
;
:
c

0
\

s
:
:
.

;
:
c

s
:
:
.
.
.
.

0
-
C

:
!

i
:
;
'

:
!

6.2 Aquation and Solvolysis of Chromium(III) Complexes 141
21.0 0.5 kcal mol-
1
and !lst = -14.2 1.5 cal K-
1
mol-I, and for the
loss of DMF 10
6
k = 9.26 s-I, aRt = 21.3 0.2 kcal mol-
1
and !lst =
-10.0 0.7 cal K-
1
mol-I. The rates are affected by changes in ionic
strength (perchlorate concentration) but an explanation was not established.
The [Cr(NH
3
hX]"+ ions (X = [Se04]2- and [H
2
As0
4
r) have been
prepared, and the rates of formation and dissociation found to be verl
rapid. These reactions proceed without metal-oxygen bond cleavage. (1 )
The trans- and cis-[Cr(NH
3
MCNht ions have been prepared from
the corresponding [Cr(NH
3
MDMSOh]3+ ions. In DMSO solution reaction
of [Cr(NH
3
MDMSOh]3+ with CN- proceeds with geometric isomerism to
give a mixture of the two dicyano products, whereas in aqueous solution
the reactions are stereoretentive. Preliminary kinetic data indicate that the
trans-dicyano isomer is more labile than the cis isomer by about one order
of magnitude, and below [H+] = 0.1 mol dm -3 the stepwise hydrolyses are
first order in [H+]. The aquations proceed with retention of configuration
trans-[Cr(NH
3
MCNht + H
2
0 -+ trans-[Cr(NH
3
MH
2
0)CN]2+ + CN-
(15)
trans-[Cr(NH
3
MH
2
0)CN]2+ + H
2
0 -+ trans-[Cr(NH
3
MH
2
0h]3+ + CN-
(16)
[equations (15) and (16)]. At 298.2 K, reactions (15) and (16) are character-
ized by second-order rate constants of -8 x 10-
2
and
_10-
4
dm-
3
mol-
1
s-t, whereas for the analogous reactions of the cis
isomer both reactions have approximately the same rate constant of 5 x
10-
3
dm
3
mor
1
S-I. The unusual greater lability of the trans isomer is
attributed to the trans effect of the CN- ion, which also accounts for the
similar rates of aquation of the two cis species. (15)
The rate of aquation of trans-[Cr(enhF
2
t ion has been measured in
concentrated HCI0
4
(6.1-11.9 mol dm -3), H
2
S0
4
(4.1-14.1 mol dm -3) and
HN0
3
(3.1-14.6moldm-
3
), and cis-[Cr(bipyhF
2
t ion in concentrated
HCI04 The reactions proceed with retention of configuration to give the
Scheme 2
rapid

-
2+
[FILL) crFH] + H
2
0
mono-aquo products. The basicity of trans-[Cr(NH3)4F2r was also
examined. From the kinetic studies, plots of (log k-Iog[acid]) against log a
w
are linear with slopes in the range -0.4 to -1.04. It is concluded that
water participates in the rate-determining step as a proton-transfer agent.
The mechanism shown in Scheme 2 (LL = en or bipy) is postulated.
Catalysis by added sodium fluoride was also observed, a maximum
rate being found at a fluoride: complex ratio of -S. This catalysis is
attributed to either F- or HF attacking the coordinated HF in transition
states such as those shown in Structures 3 and 4.
[FI LLI
2
Cr- F -H ] 2+ [FILLl
2
Cr- F-H-- F r
I I
I I
I I
H-F
3 4
General acid-base catalysis is not involved since the addition of other
salts had no effect on the reaction rates. The [Cr(LLhF(OH
2
)](CI0
4
h
complexes with LL = 1,3-pn, bipy, or phen were isolated.(16)
Data obtained for the aquation of cis-[Cr(enh(OH
2
)Xf+ ions (X = CI,
Br, I) in 0.1 and 1.0 mol dm -3 HCI0
4
and I = 1.0 are collected in Table
6.6. The greater rates at lower [H+] could be attributed either to base
hydrolysis, or to the participation of the hydroxy-conjugate base, cis-
[Cr(enh(OH)Xr. The latter is most likely.m.1s)
The tetraazamacrocyclic ligand complexes [Cr(L)X
2
r have been pre-
pared with a cis geometry when L = [12]aneN
4
(X = CI or NCS), both cis
and trans geometries when L = 1,4,7,1l-[14]aneN
4
(X = CI), and only a
trans configuration when L = [lS]aneN4 (X = CI). Aquation rates for cis-
[Cr([12]aneN
4
)Chr ion are reported to be unusually rapid, and complete
kinetic investigations of all these systems are underwayY9)
The kinetics of the first stage in the acid hydrolysis of trans-[Cr(L)Cht
ion (L = C-meso-S,7,7,12,14,14,-hexamethyl-1,4,8,1l-tetraazacyclotetra-
decane, tet-a) having the R S S R configuration has been reported.
Table 6.6. Activation Parameters at 298.2 K for the Aquation of cis-
[Cr(enMOH
2
)XF+ Ions at Two Acidities and 1= 1.0 (Data from Refs. 17 and 18)
[H+] = 0.1 mol dm-
3
[H+] = 1.0 mol dm-
3
X
AHt/kJmol-
1
AStIJK-
1
mol-
1
AHt IkJ mol-
1
ASt IJ K-
1
mol-
1
Cl 88.8 0.7 -36.5 2.2 92.1 1.8 -25.7 0.6
Br 73.3 0.2 -70.8 0.6 75.2 0.5 -65.5 1.5
I 85.6 1.7 -12.15.7 87.7 2.3 -5.5 7.8
6.2 Aquation and Solvolysis of Chromium(III) Complexes 143
Aquation proceeds with retention of configuration, and at 298.2 K, the
rate constant and activation parameters are 10sk == 1.26 s -t, dB* ==
92.6 2.4 kJ mol-
1
and as; == -37 5 J K-
1
mol-
1
. The reaction was
studied in H
2
S04 solution for solubility reasons. The analogous cobalt(III)
complex is characterized by dB* == 107 kJ mol-
1
and as* ==
+54 J K-
1
mol-t, indicating a more associative mechanism for the
chromium(III) complex. (20)
The kinetics and mechanism of the cleavage of the Cr-C bond in
[Cr(EDTA)(CR
1
R
2
0H)]2- ions (Rt. R2 == H or Me) have been reported
(see previous discussion of analogous [(H
2
0)sCr(CR
1
R
2
0H)]2+ ions(6-9.
When either R1 == R2 == H or R1 == R2 == Me, the pseudo-first-order rate
constant increases linearly with [H+], and k == ko + k1[H+]. However, when
R1 == Hand R2 == Me, the more complex acid dependence, k ==
(k
o
+ k
1
[H+])/(1 + Q[H+]) is observed, with Q == 2 X 10
3
at 298.2 K.
Values of ko, kt. and their associated activation parameters are collected
in Table 6.7. Comparison with the results for [Cr(H
2
0)s(CR
1
R
2
0H)]2+
ions indicates that for the k 1 pathway the uncoordinated carboxylate arm
of the coordinated EDTA acts as an internal electrophile to the chromium-
bound carbon atom. Whereas aquation of [Cr(EDTA)Xr- ions (X ==
MeCO
z
, NCS-, etc.) proceeds 10
7
_10
9
times faster than aquations of
[Cr(H
2
0)sXr+ owing to the uncoordinated carboxylate arm of EDTA
acting as an internal nucleophile, when X == CR
1
R
2
0H, it is found that
the values of ko are similar for both EDTA and penta-aquo complexes.
This is interpreted by postulating electrophilic attack by H of a water
molecule, or H30+, at the C atom of the hydroxyalkyl group, with the
uncoordinated carboxylate arm playing no part. However, values of k1 for
[Cr(EDTA)(CR
1
R
2
0H)f- are 10
4
-10
6
times as large as corresponding
values for the penta-aquo series, and electrophilic attack by the H of the
adjacent pendant C0
2
H group is postulated. (21)
Rate data obtained for the dissociation of [Cr(LLh(OH
2
)Xr+ ions
(X == NCS- or N3", imidazole, py, nicotinate ion), LL == Schiff bases (salen
and acacen), are collected with data for their formation reactions in Section
Table 6.7. Rate Constants and Activation Parameters at 298.2 K and 1=1.0
(LiCI0
4
) for the Following Reaction (Data from Ref. 21): [Cr(EDTA)
(CR
1
R
2
0H)P- + H30+ -+ [Cr(EDTA)OHJ- + organic products
104kO/ Mlt/ Ilst/
kd
Mlt/ Ilst/
RI Rz
s
-I
kJ mo)-I J K-
1
mo)-I dm
3
mo)-I 8-
1
kJ mo)-I J K-
1
mo)-I
H H 2.52 0.22 74.2 -65 256 98.6 132
H Me 13.5 1.1 81.9 -25 73.5 81.8 65
Me Me 1383 80.9 -10 176 72.9 43
6.3.2.1. Axial ligand substitutions of tetraphenylporphinatochromium(III)
chloride are discussed in Section 6.3.2.2.
6.2.2. Multidentate Leaving Groups
The observed pseudo-first-order rate constants for the aquation of
cis-[Cr(malh(OH
2
hr ion in acidic solution containing metal ion catalysts
(M =: Cu
2
+, Ni
2
+, Co
2
+, or Zn
2
+) varies as shown in equation (17).
k =: kH[H+] + kM[M2+] (17)
Values of the second-order rate constants and the associated activation
parameters are collected in Table 6.8. The metal ion catalysis arises from
chelation by the coordinated malonate ion as shown in Structure 5, values
[
I H2012Imal)(( O-c;o> Mn+]

5
of kM paralleling the known stability constants for chelation by dicarboxy-
lates.(22) This chelation is believed to occur despite the presence of the
backbone methylene group, and is of relevance to the proposed mechanism
for the isomerization of [Cr(malh(OH
2
hr ion where ion-pair formation
with metal ions was reported not to occur. (23)
Tris(Chelates)
An SN2 mechanism is reported for the exchange of 14C-Iabeled ethane-
1,2-diamine (en) with [Cr(enh]3+ ion in N -methyl formam ide solution.(24)
Ligand exchange with [Cr(EhNCSh] proceeds in DMF solution with
activation parameters I::Jlt =: 15.9 kcal mol-
1
and I:lst =: -23.9 cal
K-
1
mol-\ but in dioxane solution the reaction is very slow below 90c.(25)
6.2.3. Bridged Dichromium(III) Complexes
A second dimer of formula [(H
2
0)sCrOHCr(OH
2
)s]5+ has been found
In addition to the well-known dihydroxy-bridged species
Table 6.S. Rate Constants at 313.2 K, and Associated Activation Parameters for
the Acid-Catalyzed and Metal-lon-Catalyzed Aquations of cis-[Cr(maIMOH2)2r
Ion (Data from Ref. 23)
Catalyst
H+
Co
2
+ Ni
2
+ Cu
2
+ Zn
2
+
10
4
kldm
3
mol-I S-I
13.0 8.27 10.32 91.19 5.10
M/'/kJmol-
1
85.3 37.2 73.3 26.5 59.9
as'/J K-
1
mol-I
-30.9 -188 -71 -202 -120
6.3 Formation of Chromium(III) Complexes
145
[(H
2
0)4Cr(OHhCr(OH
2
)4t+. The singly bridged species is favored at high
acidities, with approximately equal amounts of the two species present at
-2 mol dm -3 [H+]. Magnetic measurements and esr spectra were obtained
for both complexes. (26)
6.3. Formation of Chromium(III) Complexes
6.3.1. Reactions of [Cr(H
2
0)6P+
Reaction of [Cr(H
2
0)6]3+ ion with glycine has been studied kinetically
between pH 3.40 and 4.50 where the predominant ligand species is the
+
zwitterion, NH
3
CH
2
C02" (Scheme 3). From studies between 45 and 55C,
Scheme 3
3+ + Kip
[Cr(H
2
0)6] + NH
3
CH
2
C02" ion pair
ion pair [(H20hCr02CCH2NH3]3+ + H
2
0
the interchange rate constant (k) is characterized by lll/* = 58 kJ mol-
1
and as* = -129 J K-
1
mol-I, and the ion-pair formation constant, Kip, by
!ur = 23.1 kJ mol-
1
and aso = -181 J K-
1
mol-I. An Ia mechanism is
favored in view of the low lll/*(k) value and large negative IlS* value (in
comparison, for H
2
0 exchange /lH* = 109 kJ mol-
l
and as* =
+ 11.7 J K-
1
mol-
I
).(27) Very similar conclusions were reached for the reac-
tion of [Cr(H
2
0)6]3+ ion with 2-picolinic acid in 30% vjv H
2
0jEtOH.(28)
[Cr(H20hLLH]3+ ions containing O-bonded amino acids (LLH) are
the products of the inner-sphere reduction of [Co(NH3MLL)]2+ ions by
Cr(aq)2+ ion.(29)
The formation of K3[Cr(CNhOH] is reported from the reaction of
KCN with [Cr(NH3hCI]Ch followed by a Sephadex gel column separ-
ation.(30)
6.3.2 Formation of Mixed-Ligand Complexes
6.3.2.1. Ammine and Amine Complexes
Anation of [M(NH
3
hOH
2
]3+ (M = Co or Cr) by NCS- ion has been
studied in aqueous-organic solvents (alcohols, dioxane).(31)
The rapid formation and dissociation of [Cr(NH
3
)sXr + (X
n
- = SeO
H
2
As0
4
) was described previously,(14) as was the formation of cis- and
trans-[Cr(NH
3
MCNht ions,(1S) and tetraazamacrocydic ligand complexes
of the type [Cr(L)X
2
t (X = CI or NCS)Y9)
In an interesting paper the relatively rapid reactions of Schiff
base complexes of the type [CrL(OH
2
ht [L = N,N'- bis-
(salicyclideniminato )ethane-1 ,2-diamine, salen, or N,N' -bis(pentane-2,4-
diiminato)-ethane-1,2-diamine, acacen] with NCS-, N
3
, py, imidazole, and
nicotinic acid were investigated. The pseudo-first-order rate constants were
found to be in the range 0.01-3 S-1 with an incoming ligand concentration
between 0.013 and 0.5 mol dm -3. This remarkable lability is attributed to
a ground state distortion, with one of the water molecules more weakly
coordinated to Cr(I1I) than the other. This distortion is revealed by an X-ray
structure of the salen complex, and at high pH deprotonation of one
coordinated water molecule leads to dissociation of the other to give the
five-coordinate complex [Cr(salen)OH]. Kinetic studies of the formation
reactions as a function of [H+] were consistent with the mechanism in
Scheme 4. The rate and equilibrium constants are collected in Table 6.9.
Scheme 4
kl
[Cr(L)(OHzht + x
n
- [Cr(L)(OH
2
)X](1-n)+
[H+111 K. Ll
k
[Cr(L)OH] + x
n
- [Cr(L)(OH)(X)r-
L2
Table 6.9. Rate and Equilibrium Data Associated with Scheme 4 at 303.2 K and
1= 1.0 (LiCI0
4
) (Data from Ref 32)
102kt/

kt/
107k2Ka/
Kt/
x
n
-
S
-I
mol dm-
3
S-I dm
3
mol-I S-I
S
-I
dm
3
mol-I
L = salen
NCS-
1.0 5.1 0.15 5.1 14.6
N3
0.82 1.2 0.21 0.23 25.6
py 0.21 1.4 0.21 0.21 100.0
Imidazole 0.75 1.6 0.53 55.0 70.7
3-pyCOZ- 8.3 3.2 0.16 0.85 1.9
L = acacen
NCS-
6.5 4.3 0.18 14.6 2.8
N3
1.2 98 0.11 1.2 0.9
py 7.9 10.5 0.24 4.4 3.0
6.3 Formation of Chromium(llI) Complexes 147
The values of k 1 are not very sensitive to variations in the incoming ligand,
whereas the k2Ka values vary markedly (by >275 for the salen complexes).
The reasonable conclusion is that an Id mechanism applies to [Cr(L}-
(OH
2
ht substitutions, and an associative mechanism for [Cr(L)OH]. The
variation in the k2Ka values parallels the known variation in the
nucleophilicities of the incoming ligands. (32) It is interesting that the effect
of ligand environment upon the rates of water exchange in complexes of
the type [Cr(L)(H
2
0)n]m+ are not nearly so pronounced for other ligands
than salen and acacen. Thus compared with [Cr(H
2
0)6]3+ for which k
ex
=
4.2 X 10-
7
s-t, when L = (NH
3
)5, k
ex
= 9.6 X 10-
5
S-1 and when L =
cyclam or (CN)4 relatively similar exchange rates are observed.(32) It would
appear that distortion of the metal ion environment can significantly over-
come the crystal-field activation energy which normally reduces the rate
of Cr(lll) substitutions, and this observation is of relevance to the entactic
state of many metal ions in metalloenzymes. The labilization is similar to
that seen in [Cr(porphyrin)(OH
2
h] complexes.
Ammination of trans-[Cr(I,3-pnhBrFt with liquid ammonia yields
pure trans-[Cr(I,3-pnh(NH
3
)F]2+ ion. The X-ray structure of the product
is reported. (33)
The rates of SN2 methylation of coordinated thiolates, selenates and
sulfenates (e.g., [Cr(enh(SCH
2
CH
2
NH
2
)]2+) by Mel have been
measured. (34)
6.3.2.2. Porphyrins
A D mechanism has been established for substitution reactions of
chloro(tetraphenylporphinato)chromium(III), [Cr(TPP)(L)(CI], where L
(and incoming ligand X) includes methylimidazole (Melm), py, and PR
3
(R = Ph, C
2
H
4
CN, prt
k
[Cr(TPP)(L)X] [Cr(TPP)CI] + L (18)
k2
[Cr(TPP)CI] + [Cr(TPP)(X)CI] (19)
The five-coordinate intermediate shows considerable discriminating
ability (k3/k2) in toluene solution, as shown by the data in Table 6.10. The
relative reactivities with Melm, py, P(OPrih, P(C
2
H
4
CNh, and PPh
3
are
1030: 600: 40: 5: 1. The stabilities of the [Cr(TPP)(L)X] complexes vary
with L in line with the proton basicities, and a plot of In K against pKa of
HL + has a slope of 0.9 and a correlation coefficient of 0.99. The Cr(lIl)
is, therefore, to be regarded as "hard" in such complexes with little 1T
bonding to L. The relatively slow rate of dissociation (k 1) of PPh
3
is
surprising, and is attributed to steric effects. Loss of chloride ion only occurs
Table 6.10. Kinetic and Thermodynamic Data in Toluene Solution at 298.2 K
Associated with Equations (18) and (19) (Data from Ref. 35)
L X
ki/s-l
k3/ k 2
logK
PPh
3
MeIm 4.6 0.3 1030 200 4.S 0.3
P(OPrih Me 1m 95 12 24 5 4.1 0.6
P(C
2
H4CNh MeIm SO 10 -200 5.3 0.5
py MeIm 5.0 O.S 1.7 0.4 2.5 0.1
PPh
3
py 3.6 0.5 600 2.6 0.2
P(OPrih py 904 14 1.9 0.1
P(C2H4 CNh py 90 10 3.1 0.3
P(C2H4CNh PPh
3
76 15 0.5 0.2
in more polar solvents (e.g., acetone) when there is a good trans-Iabilizing
ligand such as a phosphine or cyanide ion present. (35)
A study of the reaction of CN- and NCS- (X-) ions with meso-tetra(4-
N -methylphorphine)diaquochromium(III) ([Cr(P)(OH
2
h]5+) is reported
in the range pH 1-13 and over a 20C temperature range. The [Cr(P)
(OH
2
hf+, [Cr(P)(OH
2
)OHt+, and [Cr(P)(OHh]3+ ions are all involved
(formation rate constants kh k2' and k3 and dissociation rate constants
Lh k-2' L
3
, respectively). The pKa's are 6.74 and 10.66 at 298.2 K, and
for the reaction with NCS- at 303.2 K, 10
3
k
1
= 1.19 dm
3
mol-
1
S-1 (MI* =
84 kJ mol-t, AS* = -23 J K-
1
mol-
1
), 10
3
L
1
= 0.42 S-1 (AH* =
62 kJ mol-
1
, AS* = -100 J K-
1
mol-
1
), k2 = 1.44 dm
3
mol-
1
s -1 (AH* =
61 kJ mol-I, AS* = -30 J K-
1
mol-I). The data obtained for the reaction
with CN- ion are very similar. The [Cr(P)(H
2
0hf+ ion is -400 and 25
times as labile as [Cr(H
2
0)6f+ and [Cr(NH
3
hOH
2
]3+, respectively, toward
NCS- anation, and the conjugate base [Cr(P)(OH)(OH
2
)t+ is 5.4 x 10
3
times as labile as [Cr(P)(H
2
0h]5+ ion. An Id mechanism is proposed.(36)
6.3.3. Formation of Cr(III) Complexes from Cr(II) or Cr(O)
Reaction of [Co(NH
3
)4(O-N)]2+ ions (O-N = amino acid) with
[Cr(H
2
0)6]2+ gives(29) the O-bonded amino acid complexes [(H
2
0hCrO-
NH+]3+.
The [Cr(bipy)(acac)(OH
2
h]2+ ion is major product of chromous
reduction of [Co(bipyh(acac)]2+, and the transition state or intermediate
(6) is postulated to account for this.(37)
cis-[Cr(bipyh(H
2
0)CI]2+ ion is the product of the slow oxidation of
CrClz and bipy. (38)
Photolysis of [Cr(CO)6] in the presence of tetrachloro-o-quinone gives
[Cr(02
C
6
CI
4
h]. (39)
6.4 Chromium(III) Photochemistry 149
6
6.4. Chromium(III) Photochemistry
Two useful reviews have appeared. One general review deals with the
photochemistry and photophysics of chromium(III), (40) and the second
specifically with the advances in the photochemistry and photophysics of
polypyridyl complexes of chromium(III). (41)
6.4.1. Ammine Complexes
Using glycerol/H
2
0 mixtures (:;:;65 wt%), the viscosity dependence of
the photoaquations of [Cr(NH
3
)6]3+, [Cr(NH
3
)sNCS]2+, [Cr(NCS)6]3-, and
[M(CN)6]3- (M = Co or Cr) have been investigated. The pressure depen-
dence of the photolysis of [Cr(NH
3
)sNCS]2+ (1 :;:; P :;:; 1.5 kbar; 1 < Tf <
30 cP) was also studied. (42) Significant cage recombination occurs during
the photosubstitution of NH3 in [Cr(NH
3
)sNCsf+ and [Cr(NH
3
)6]3+ in
water, whereas photo catalyzed loss of CN- or NCS- proceeds without
significant cage effects. Cage recombination proceeds with the mechanism
(S = solvent) shown in Scheme 5. With this scheme the quantum yield is
Scheme 5
s kg
[ML5dcage ---... [ML5S] + L
given by
 - k6 kg _ ( kg )
- k5 + k6 k7 + k8 - 0 k7 + k8
<1>0 is the "primary" quantum yield for bond cleavage and is assumed to
be viscosity independent. In pure water = <1>0 and cage effects are negli-
gible. kg decreases approximately inversely with increasing viscosity (k7
const), and for the ammine complexes an fa mechanism is most probable.
For [M(CN)6]3- and [Cr(NCS)6]3-, <1>0 and k7 k
8
An fd mechanism
is most likely in these cases. For [Cr(NH
3
)sNCS]2+ the volume of activation
associated with k6 (Le., from plots of In <1>0 versus pressure) is estimated
to be -9.5 cm
3
mol-t, close to the value in pure water (-9.8 cm
3
mol-I).
At high viscosities the dependence of In on pressure is complex with
maxima observed around 1 kbar. The reason for this is uncertain. (42)
Ligand-field photolysis of trans-[Cr(NH
3
MDMF)C1]2+ ion leads
largely to the loss of DMF, with some loss of NH3 and Cl- as well. From
the wavelength dependence of the quantum yields, the 4E and upper 4D2
states are inferred to be the main precursors to aquation of the axial ligands,
and of NH
3
, respectively. Replacement of DMF and Cl- occurs with
complete trans -. cis isomerization, although charge transfer photolysis is
less stereoselective. (43)
6.4.2. Amine Complexes
The rather contentious question of the relative importance of either
doublet or quartet states in the photoaquation of [Cr(enh]3+ ion has been
examined by three groupS.(44-46) The evidence reported earlier in favor of
a slow reaction from the doublet state(47) has been reexamined by Kirk,
who concludes that the involvement of a quartet state is more likely.(44)
Similarly, from a study of the photoaquation of A-[Cr(enh]3+ between 365
and 685 nm in aqueous acidic solutions, it is concluded that the lowest
lying quartet state is photoreactive, with back intersystem crossing from
the lowest doublet state to the quartet state responsible for the delayed
reaction.(45) The wavelength-independent quantum yields of the three
products, A-cis, D.-cis-, and trans-[Cr(enh(enH)(H0
2
)]4+ are 0.10, 0.03,
and 0.24, respectively.(45) Very recently, however, good evidence in favor
of doublet state reactivity has been found. Irradiation at 669.2 nm populates
the 2 Eg state and enhances the reaction efficiency by 50%. At this
wavelength there is little or no competitive absorption from the quartet
state.(46)
The quantum yields for the photoaquation of 12 polypyridyl
[Cr(LLh]3+ ions (LL = bipy, 4,4'-Me2-bipy, 4,4'-Ph
2
-bipy, phen, 5-Cl-
6.6 Base Hydrolysis of Chromium(III) Complexes 151
phen, 5-Br-phen, 5-Me-phen, 5-Ph-phen, 5,6- and 4,7-Me2phen, and
4,7-Ph
2
-phen) have been determined at 22C. The photophysics of these
species was examined in some detail.(48) Oxidation of chromium(II) poly-
pyridine complexes by [S205f- leads to luminescence emission from the
2g state of the corresponding chromium(III) complexes. (49) Very low
quantum yields (0.02 and 0.05) are reported for the ligand-field photolyses
in the first d-d band of [Cr(NCS)4Lr ions (L = bipy and phen, respec-
tively). (50) Ligand-field laser irradiation of either racemic [Cr(oxh(phen)r
or [Cr(ox)(phenht in the presence of d-cinchonine or I-cinchonidine
hydrochloride leads to a relatively rapid shift in a chiral equilibrium between
the two enantiomers, which is opposite in direction to that induced by the
usual Pfeiffer effect of these systems in the dark. (51)
6.4.3. Other Chromium(lII) Complexes
Good evidence, including esr absorption, and circular dichroism
spectra, has been reported for the formation of Cr(V)-nitrides from the
uv photolysis of azidochromium(III) complexes such as [Cr(L)N3r- (L =
edta
4
-, nta
3
-, salen, or d-valine-N,N -diacetate ion).(52,53)
[LCr(III)(N
3
)(OH
2
)r [LCr(V)N(OHh] + N2 (20)
[LCr(III)(N
3
hf- [LCr(V)N(OHh)r + N2 + N3 (21)
6.5. Isomerization and Racemization Reactions
The trans-cis isomerization of K[Cr(oxh(OH
2
hr ion has been
examined in aqueous/organic solvents (EtOH, dioxane, Me2eO). The
first-order rate constant decreases with increasing concentration of organic
solvent. Both chelate-ring-opening and twist mechanisms are involved. (54)
This reaction is also catalyzed by ion pairing with Mg2+ ions. (55)
From studies of the inversion reaction of A-( + )s89-[Cr(trien)(ox)t in
hydrochloric acid, to give - )s89-cis-a-[Cr(trien)Clzt, the oxalato com-
plex is now believed to have the cis-{3 configuration. This is a rare example
of an acid-catalyzed isomerization of this type.(56)
A-( + )589-[Cr(trien)(ox)t + HCl --. - )ss9-cis-a-[Cr(trien)Clzt (22)
6.6. Base Hydrolysis of Chromium(III) Complexes
The SN 1CB mechanism is favored for the base hydrolysis of trans-
[Cr(L)Clzt ion (L = C-meso-5,7,7,12,14,14-hexamethyl-1,4,8,1l-
tetraazacyclotetradecane, teta). For loss of the first Cl- ion, rate =
k[complex][OH-], with k = 145 dm
3
mol-
I
s-\ Mit = 113 3 kJ mol-I,
and !1st = 179 6 J K-
I
mol-
I
at 298 K. The analogous cobalt(III) com-
plex undergoes base hydrolysis much more rapidly (k = 1.5 x
10
6
dm
3
mol-
I
S-I), but despite the fact that the ratio of the rate constants
k Co / k Cr is -10
4
for tetraamines and 10
3
for pentamines, the large positive
!1st value fits with the expectation of an SN 1 CB mechanism. Comparison
of trans-[Cr(teta)Cht with trans-[Cr(cyclam)Cht shows steric acceleration
by C-methyl substitution in line with an SN1CB mechanism.(57) Loss of the
second Cl- ion from the teta complex occurs at a similar rate to loss of
the first Cl-, and initial rates were used in the kinetic analysis of the first
stage.
6.7. Solids
Enthalpies of activation have been determined for the dehydration,
dehydrohalogenation, and isomerization of cis- or trans-
[Cr(LL)zX
2
]XH
2
0 (X = CI or Br; LL = d,l-2,3-butanediamine, 1,2-cyclo-
hexanediamine, and 2,4-pentanediamine). A bond-rupture mechanism is
proposed for the isomerization, the opposite conclusion to an earlier pro-
posal that a twist mechanism is involved. (58-59)
Differential thermal analysis and differential scanning calorimetry have
been used to study the formation of cis-[Cr(L)z(S206)F] from trans-
[Cr(L)z(OH
2
)F]S206 (L = en, 1,3_pn).(60)
The crystal structure and thermal behavior of (+ h89-[Cr(enh]Ch is
reported. (61)
6.8. Other Chromium Oxidation States
6.8.1. ChrOm ium (II)
The kinetics of the Zn
2
+ -induced dissociations of [CrL
3
r+ (L =
4,4'-diMe-bipy and 5,5'-di-Me-bipy) have been studied.(62)
6.8.2. Chromium(V)
Electron spin resonance evidence for the formation of Cr(V)-nitrides
was described previously. (52.53)
Chapter 7
and Above: Cobalt
The level of activity in this area remains high, with a considerable volume
of interesting work appearing, particularly in the area of the reactions of
coordinated ligands. Review articles of interest include a general discussion
of the chemistry of cobalt(III) complexes(l) and a review dealing with
activation volumes and their application to the determination of reaction
mechanisms. (2)
7.1. Aquation
The application of activation volumes (A V*) as a mechanistic probe
in inorganic reactions has attracted considerable interest in recent years. (2)
Pentaamminecobalt(III) complexes have been well studied, mainly with
anionic leaving groups. The negative A V* values generally observed for
anionic leaving groups suggest that solvent electrostriction changes in
forming the activated complex contribute significantly to A V*.
Lawrence(3) has recently reported activation volumes for the aquation
of alcoholpentaamminecobalt(III) complexes (see Table 7.1). Partial molar
153
154 7. Substitution Reactions-Coordination Nos. 6 and Above: Cobalt
Table 7.1. Activation Volumes and Calculated Reaction Vo/umes(.ll for Aquation
of [Co(NH
3
)s(OHR)P+ Complexes and Partial Molar Volumes of Complex Ions
and Ligands in Aqueous Solution at 25C
av*, V V
Ligand
cm
3
mol-
1
av (complex ion) (ligand)
OH
2
+1.2 0.0 60.3 18.0
OHCH
3
+2.2 + 1.6 78.8 38.1
OHCH
2
CH
3
+2.9 +2.2 95.2 55.1
OHCH(CH
3
h +3.8 +2.9 111.3 71.9
volumes CV) of the CF
3
SO
J
salts of the complexes and values of V for the
free alcohols are also included in the table. The reaction volume is
defined as in equation (1).
V = {V[Co(NH
3
)sOH
2
]3+ + V(OHR)}
(1)
Although V (alcohol) increases fourfold through the series studied, V
t
is essentially unchanged. The V values calculated from equation (1) closely
approximate the determined values of V
t
. The small range of V
t
values
observed with the various alcohol ligands supports the view that electro-
structure effects or solvation changes in forming the activated complex are
minor in this series.
For the acid-independent and acid-dependent aquation pathways of
[Co(NH
3
)sS04t, the respective volumes of activation (at zero pres-
sure) and (pressure averaged over 100 MPa) are -18.3 and
-3.5 cm
3
mol-
1
at 35C and -19.7 and -3.9 cm
3
mol-
1
at 55 and 1=
1.0 M.(4) The temperature dependence of can be accounted for in
terms of solvational change indicated by its pressure dependence. The work
also questions the common supposition that the molar volumes V of the
penta- and hexacoordinate ammine complexes of the same metal ion are
equal and suggests that there is a difference of 17-20 cm
3
mol-
1
for the
cobalt(III) case.
The pressure, temperature, and pH dependence of the aquation rates
of a range of trans complexes, [CoN
4
X
2
t [X = CI and N4 = (NH
3
)4; (enh;
RS-2,3,2-tet; RR,SS-2,3,2-tet; (Meenh; (Etenh; (Prenh, 3,2,3-tet; 2,3,2-
tet; cyclam and X = Br, N4 = (enh; 2,3,2-tet and 3,2,3-tet] have been
determined.(S) Values of V
t
for all the dichloro complexes including
cis-[Co(enhCht averaged -1.4 1.0 cm
3
mol-
1
interpreted in terms of
an Id mechanism. The somewhat more positive V
t
values for the dibromo
7.1 Aquation 155
complexes are also consistent with this mechanism. The aquation of the
complexes trans-[Co(NH
3
MCN)Xt (X = CI, Br, I, N
3
, or DMSO) are also
considered to involve a similar mechanism, although in this case significantly
more associative character is suggested.
Aromatic sulfonamides are well known to be strong inhibitors of
carbonic anhydrase, and there is general agreement that the sulfonamide
is complexed as the anion to Zn(II). Very few simple inorganic sulfonamide
complexes have been prepared, but the pentaammine complexes of
NH
2
S0
2
NH-, p-CH
3
C
6
H
4
S0
2
NH-, and P-N0
2
C
6
H
4
S0
2
NH- have now
been characterized. (6) The rate expression for the hydrolysis of
[Co(NH
3
)sNHS0
2
NH
2
]2+ has the form, rate = k
2
[H+]/(K
a
+ [H+]). At
25C (I = 1.0 M) k2 = 1.41 X 10-
2
S-1 with lli* = 21.7 kcal moC\ AS* =
5.5 cal K-
1
moC
1
and Ka = 0.58 M. The hydrolysis kinetics of the aromatic
sulfonamido complexes follow the same rate law if Ka [H+]. The unusually
large aquation rate constants are attributed to N-protonation of
[Co(NH
3
)sNHS0
2
]2+ followed by rapid release of the neutral ligand.
The syntheses of [Co(NH3)sOS02R] (CI0
4
h (R = CH
3
, CF
3
, p-
N0
2
C
6
H
4
) have also been described.(7) Complexes of the type
[Co(NH
3
)sXr+ have been prepared with a very large range of substituents.
Specific rate constants for aquation range from _10-
9
to 10-
4
s -1 at 250C, (6)
while base hydrolysis involving the metal center range from
_10-
6
to 6 M-
1
S-1 at 25C.(S) The extreme lability of the sulfonate com-
plexes is seen in the aquation (k
aq
) and base hydrolysis (k
OH
) rate data
shown in Table 7.2. These results extend the range of [Co(NH
3
)sXr+
reactivity by about 10
5
-fold for base hydrolysis and about 10
2
-fold for
aquation. The triftate complexes are of considerable value in synthetic work
due to the lability of the triftate ligand. (9)
The two geometrical isomers of N-rac-trans-
[CoQ(Me6[14]diene)N02t, 1 and 2, have been isolated in which the
chloride ligand lies syn or anti to the two chiral N-H groupS.(lO) The syn
Table 7.2. Values of kaq and kOH for
Sulfonatopentamminecobalt(III) Complexes, (6.8)
[Co(NH3)sOS02Rj2+ at 25C and 1= 1.0 M
(NaCI0
4
)
k
aq
,
kOH'
R S
-I
M-1s-
1
CH
3
2.0 X 10-
4
55
CF
3
2.7 x 10-
2
_10
6
P-N02C6H4
6.3 X 10-
4
270
H Cl H N0
2
I I H I I H
N, -r=,N
N" -I?N

N I N N I N
I
I
N0
2
Cl
syn anti
1 2
isomer aquates slowly in 0.1 M HN0
3
with ka1 = 4.8 X 10-
4
s -1 at 25C
(MIt = 75.3 kJ mol-I, = -55 J K-
1
mol- ), while the anti isomer
aquates very rapidly (tl/2 < 10 s) at 25C. These results can be rationalized
in terms of the macrocycle folding toward, or against, the leaving group
in the transition state of the reaction. Steric compression by the gem-
dimethyl groups is also considered to facilitate rapid hydrolysis of the anti
isomer. The ability of a macrocyclic ligand to fold appears to have important
consequences regarding the rates of aquation of acido-complexes and the
stereochemistry of the final product obtained.
The RSSR- and the RRRR (SSSS)-diastereoisomers of trans-
[CoClz(cyclam)t are shown in 3 and 4, respectively, and neither of these
H Cl H
1-1-.1

N/I "N

H I H
Cl
RSSR
3
, Cl H .... fold
, I I .... "
"'N- -N" ....
Gfco:)
N_ I _N
". ",'" I',
.... I H "
Cl .... fold
RRRR(SSSS)
4
complexes is subject to. steric compression by ring substituents. Both
diastereoisomers have equivalent axial sites; however, the RSSR
diastereoisomer cannot fold (k
aq
= 1.1 x 10-
6
s-1 at 25C), while the
RRRR (SSSS) diastereoisomer has two possible fold axes and thus under-
goes rapid aquation (k
aq
= 1.75 x 10-
3
s-1 at 25C) (folding of 14-
membered rings requires the nitrogens lying trans to each other to have
the N-H groups lying on the same side of the macrocyclic plane).
Significantly the RSSR diastereoisomer gives 100% trans-
[CoCI(cyclam)OH
2
t, while the RRRR (SSSS) diastereoisomer gives a mix-
7.1 Aquation 157
ture of 75% trans- and 25% cis-[CoCI(cyclam)OH
2
]2+, which subsequently
isomerizes to 100% cis isomer. The concept can be used to rationalize the
aquation rates of diastereoisomeric complexes of cobalt(III) macrocycles.
The trans-[Co(enh(DMSO)Clf+ ion aquates rapidly(11) at 25C in
0.1 M HCI0
4
with kaq = 8.7 X 10-
4
S-I. The release of chloride is not a
competitive reaction. Some 70.5% of the trans-aquo-chloro complex is
initially produced. Subsequent to aquation of [Co(enh(OH
2
)Clf+ the
isomers interconvert (k
isom
= 9.90 X 10-
5
s-l) to give 79% cis-isomer at
equilibrium. These results agree with those obtained independently for cis-
and trans-[Co(enh(OH2)CI]S206H20, where k
isom
= 10.4 X 10-
5
s-1 to
give 79% cis isomer. It is concluded that all the aquations are dissociative
involving a common reactive pentacoordinate intermediate.
Comments on the synthesis and aquation of cis- and trans-
[Co(enh(N0
2
)Clr have been publishedY
2
) Although various papers men-
tion the preparation of these complexes, they mainly refer to early work
by Werner. The synthetic problems encountered are discussed in detail.
The kinetics of aquation and base hydrolysis of cis-f3z-[CoCI(trien)-
(benzimidazole)f+ (5) have been reported. (13) In the acidity range [H+] =
0.001 M to 0.1 M, chloride is released by both aquation and base hydrolysis,
2+
,-NH2
HN ""I /" benzimidazole
( Co
HN8NH2
I
Cl
5
i.e., kobs = kaq + kOH[OH-]. At 50C, kaq = 3.4 X 10-
5
s-1 (lli* =
104 kJ mol-t, Ast = -11 J K-
1
mol-I) and kOH = 2.19 X 10
7
M-
1
S-1
(lli* = 66.4 kJ mol-t, AS* = 101 J K-
1
mol-I). The reactive conjugate is
believed to be formed by deprotonation of the "flat" secondary nitrogen
trans to benzimidazole. For Hg(II) promoted aquation kHg = 0.103 M-
1
S-1
at 35C with lli* = 72.4 kJ mol-
1
and ASt = -29 J K-
1
mol-
1
.
The kinetics of aquation and base hydrolysis of cis-[CoCl(enh(btzH)]2+
and cis-[CoCl(en)z(btzMe)]2+ complexes (btzH = benzotriazole, btzMe =
N -methylbenzotriazole) have also been studied. (14) In the range [H+] 1.0 x
10-
1
to 1.0 X 10-
3
M, the rate of aquation of the [CoCl(en)z(btzH)f+ cation
follows the relationship kobs = kl + k2K NH[H+r\ where k1 and k2 are the
rate constants of the acid-independent and acid-dependent steps and kNH
is the acid dissociation constant of the coordinated benzotriazole (the above
equation is kinetically equivalent to kobs = kaq + kOH[OH-]). The complex
cis-[CoCI(enh(btzMe)]2+ (6; R = Me) undergoes acid-independent hy-
drolysis presumably due to the absence of a labile NH proton in the
benzotriazole ring. It seems that benzotriazole deprotonation can lead to
a particularly reactive amido complex (7) and this ami do species can be
2+
6 7
formed at low pH. The kinetics of aquation of cis-[CoBr(enhNH
3
]2+ have
been studied using aqueous mixtures of ethyl alcohol, isopropyl alcohol,
t-butyl alcohol, and acetonitrileY
S
) The results indicate that nonelectros-
tatic interactions play an important role in the mechanism.
The syntheses of the new trans-solvento complexes, trans-
[Co(enh(solv)N
3
](CI0
4
h (solv = DMSO,DMF) have been describedY6)
Also, given are reliable preparative procedures for the known trans-
[Co(enhN
3
X]CI0
4
(X = Br or CI) complexes. Aquation rates obtained are
summarized in Table 7.3. The reactions are not fully stereoretentive as
previously reported (X = Br or Cl). A common stereochemistry (92%
trans-[Co(enhN
3
(OH
2
)]2+) results for both anionic (CI-,Br-) and neutral
leaving groups (DMSO,DMF).
Other studies have dealt with the aquation rates of some diacido
cobalt(III) tetramine complexes containing asymmetric tetramine
ligands, (17) activation parameters for the aquation of trans-[ Co(pnhClzt, (18)
polyelectrolyte catalysis in the aquation of [CO(OXh]3- in binary mixtures
Table 7.3. Aquation of the trans-
[Co(enYX)N
3
J"+ Ions at 25C (Ref. 16)
kaq,
X
S-I
% trans product
DMSO
6.0 x 10-
3
92 1
DMF
2.96 x 10-
4
92 2
Br
9.2 x 10-
4
91 1
CI
2.48 x 10-
4
91 2
7.2 Catalyzed Aquation
159
of H
2
0-DMF or H
2
0-DMSO,(19) and the aquation of trans-thiosulfato
containing dioximes of cobalt(III). (20)
7.2. Catalyzed Aquation
Evidence has been presented which demonstrates that the Hg(lI)- and
NO+ -induced aquations of t-[Co(tren)(NH
3
)Cl]2+ (8) and t-[Co(tren)-
(NH
3
)N
3
f+ follow different pathways, and a common intermediate of the

H2 I/CI
('-Co

I
NH3
8
type [Co(tren)(NH
3
)]3+ is not involved.(21) (The letters t and p denote
the isomers with the tertiary and primary amine center, respectively, trans
to the electronegative group X.) Saturation entry of NO.3 to give t-
[Co(tren)(NH
3
)(N0
2
)]2+ occurs as [NO.3] is raised to 1 M (48% for the
chloro complex and 35% for the azido complex). This limiting condition
is interpreted in terms of preformed ion pairs (KIP - 5 M-
1
). Second-order
rate constants for the Hg(lI)-induced aquation of p-[Co(tren)(NH
3
)Clf+
and t-[Co(tren)(NH
3
)Clf+ are 5.6 and 9.7 M-
1
s-\ respectively.
Some trans-(RR,SS)-[CoCI(3,2,3-tet)amine]ZnCI
4
salts (amine =
NH
3
, MeNH
2
, or imidazole) have been prepared and characterized by 13C
nmr. (22) Mercury(1I) aquation rates for these complexes have been deter-
mined giving 10
4
k
Hg
(25C) = 5.75, 98.4, and 37 M-
1
S-I for the above
order at I = 1.0 M. Base hydrolysis has also been studied with kOH =
3.48 M-
1
S-I (NH
3
) and kOH = 76.4 M-
1
S-I (MeNH
2
) at 25C and I =
O.lM.
Rate constants have also been obtained for the Hg(II)-assisted aquation
of ilA-cis-[CoCI(en)z(imidazole)]2+ in HN0
3
, HCI0
4
, H
2
S0
4
, and
CF
3
S0
3
H over the range of ionic strength 0.1-3.0 Mat 25C.(23) Empirical
relationships relating the rate constant (k
Hg
, M-
1
S-I) to the ionic strength
have been developed, e.g., log k
Hg
= 0.261 - 1.56 for HCI0
4
and 1=
0.1-3.0 M. investigation of the Hg(II)-assisted aquation of
[Co(NH
3
)sClf+ is one of the classic studies on the influence of low ionic
strength on a reaction between ions of like charge.
Two geometric isomers (red and violet), of [CoCI(L)(2,3-tri)]ZnCI
4
(L = en,pn,tn; 2,3-tri = 1,6-diamino-3-azahexane), have been isolated from
the reaction of [C02(L)z-(2,3-trih02](CI04)4 with HC!. (24) Structural
assignments have been made on the basis of 13C nmr spectra and by
comparison with related 3,3-tri (Le., dipropylenetriamine) complexes of
known configuration. The unsymmetrical tridentate (2,3-tri) is meridionally
coordinated with the red and violet isomers corresponding to the (R,S)-sec
NH protons being cis (9) or trans (10) to the chi oro ligand, respectively.
These assignments are supported by studies of the mercury(II)-assisted
aquation and base hydrolysis rates.
2+ 2+
H
X
X

N"'--I"/ NH2
N"-...,. /NH2
C "-Co
( Co
H/ I '-........NH
2
/ \"-.......NH
NH2 / 2
NH2 ../
NH2

red isomer violet isomer
9 10
A kinetic study of the aluminum(III)-assisted aquation of
[Co(NH3)sF]2+ has been published.(2S) The reaction is first order in the
complex and first order in [Al(III)] with k = 1.6 X 10-
3
M-
1
S-I at 25C
and I = 2.0 M. The reaction rate is independent of pH at pH values below
3, in contrast with the pH-dependent rate observed for the [Cr(NH3)sFf+-
Al (III) system.
The acceleration of the Hg(II)-induced aquation of [Co(NH3)SX]2+
(X = CI or Br) by the mucopolysaccharides chondroitin sulfate A and C
has been studied as a function of the concentration of polyion and Hg(II),
of pH, and the ionic strength. (26) Inhibition of this reaction by a number
of divalent ions emphasizes the electrostatic character of the metal-polyion
interactions when sulfate groups are involved.
The [Co(NH
3
)s(NH
2
CH
2
C0
2
H)]3+ ion aquates quantitatively to
[Co(NH
3
h(OH
2
)]3+ in 1.0-5.0 M HCl0
4
at 80c.(27) The kinetics have
been studied over a range of perchloric acid concentrations. The depen-
dence of kobs on various acidity functions suggests that an associative process
occurs by interaction of the conjugate acid of the substrate with H
2
0.
7.3. Base Hydrolysis
Studies on a variety of [Co(NH3)SX]2+ complexes have accumulated
evidence in support of a conjugate base dissociative (SNICB) mechanism
7.3 Base Hydrolysis
161
for hydrolysis under basic conditions. (28-30) The base hydrolysis of the
[Co(NH
3
)sL]3+ ions [where L = (NH
2
hCO, (CH
3
hSO, or (CH
3
0hPO] and
[(NH
3
)sCoOS0
3
t has been studied over a range of conditions.(31) For each
of the 3+ complexes, the possibility exists that O-coordination to Co (III)
might enhance the susceptibility of the ligand to nucleophilic attack by
hydroxide ion and this pathway could be competitive with cobalt-oxygen
bond cleavage. Nucleophilic attack on [(NH
3
)sCoOC(NH
2
h]3+ would give
NH3 and [(NH
3
)sCo0
2
CNH
2
]2+ and so provide a model for jack bean
urease, the nickel(II) metalloenzyme(32) which gives ammonium carbamate
as the initial product of the hydrolysis of urea.(33) Nickel(II) has been found
to promote the hydrolysis of N -(2-pyridylmethyl)urea as shown in 11.(34)
11
However, tracer studies (with 180H2) show that the three 3+ ions
cleave very largely (>97%) by Co-O bond rupture with rate =
k[(NH
3
)sCoL3+][OH-]. In the presence of azide ion, both
[Co(NH
3
)sOHf+ and [Co(NH
3
)sN
3
f+ are produced. The ratio of these
products is constant among the +3 substrates but differs from that observed
with the [(NH
3
)sCoOS0
3
t ion. The results support an SNICB mechanism
where the short-lived five-coordinate intermediate captures the atmosphere
of its immediate precursor.
Some new optically active Co (III) pentamine complexes have been
synthesized to establish if a trigonal bipyramid or a square pyramid is the
preferred stereochemistry for the five-coordinate intermediate in S N 1 CB
reactions. (35) In these species, a prochiral bidentate ligand is employed to
establish if its unique symmetry plane coincides with a plane of symmetry
in the intermediate. Coincidence is anticipated if the intermediate is a
7T-stabilized trigonal bipyramid. In the SN 1 CB process accelerated loss of
the leaving group from the deprotonated substrate is attributed to 7T-orbital
overlap of the type 2p(deprotonated N) --+ 3d
x
2 _
y
2Co(III). Stabilization will
develop as the leaving group is being removed and will reach a maximum
in the five-coordinate intermediate if its configuration is trigonal
bipyramidal and if the deprotonated nitrogen adopts a planar configuration
with the nodal plane of its 2p orbital acting as a symmetry plane of the

L
12
molecule 12. This proposal has been used to interpret the stereochemical
course of various hydrolysis reactions(36) and to rationalize the base hydroly-
sis reactivity pattern of chloropentaminecobalt(III) complexes. (37)
The complexes [Co(bamp)(dapo)Xf+ (13)(35) [bamp = 2,6-bis-
(aminoethyl)pyridine, dapo = 1,3-diamino-2-propanol, X = CI-, Br-, or
H
NH
z

If '\N-V:-J OH
- x/I
NH
z
[Co(bamp)(dapo)Xj"+
13
N
3
] were resolved with dibenzoyltartaric acid. Base hydrolysis (X = CI,
kOH = 2.9 X 10
3
M-
1
S-l; X = Br, kOH = 1.6 X 10
4
M-
1
S-l at I = 1.0 M
and 25C) occurs with full retention of configuration. As a result, JT stabiliz-
ation is not considered significant in the intermediate, possibly due to the
inability of the pyridine 7r orbitals to allow significant 7r bonding. As rapid
base hydrolysis occurs, presumably effective 7r stabilization can still take
place via deprotonated NH2 groups. The authors, however, discount this
view and consider that other (unstated) factors are responsible for stabiliz-
ation of the five-coordinate intermediate. It should be noted that the origin
of the substantial base hydrolysis rates of halo(pyridine) complexes of
+ ow
Q
I H
NG OH

(0
/1'
x)
14
(2)
7.3 Base Hydrolysis 163
cobalt(III) which could involve 7T stabilization via the pseudo-base 14 (28)
is still not fully resolved.(38)
A more detailed understanding of the conjugate-base mechanism for
the hydrolysis of kinetically inert amine complexes of cobalt(III) and
rhodium(III) is possible if liquid ammonia is used as a solvent. Such
techniques allow the separation of parameters for the pre-equilibrium step
(K
CB
) and the rate-determining step. A polyamine complex generally
contains more than one potentially acidic proton and each proton is charac-
terized by its own acidity constant (K
CB
). 2H_1H exchange rates for
the fully N -deuterated compounds [Co(NH
3
)6](Cl0
4
h, [Co(NH3)sCl]-
(Cl0
4
h, [Co(NH
3
)sF](Cl0
4
h. and trans-[CoCl
r
(RS-2,3,2-tet)]Cl0
4
in
liquid ammonia have now been measured over a temperature range.(39)
The base hydrolysis of cis-[CoCI(enh(bzmH)r+ (bzmH = benzimidazole)
has been studied over the pH range 8.3-11.6 at 25C and I = 0.1 M.(40)
The pKa for ionization of benzimidazole is 8.85 in the corresponding
hydroxy complex, and the kinetic data can be interpreted in terms of base
hydrolysis of cis-[CoCI(enh(bzm)t (kOH = 14.9 M-
1
s -1). The results pro-
vide evidence for the kinetic significance of two conjugate bases (deproton-
ated ethylene diamine and benzimidazole) in the reaction.
The base hydrolysis of cis-[CoX(enh(etaH)r+ (X = Cl or Br, etaH =
2-aminoethanol) has been investigated in detail. (41) The hydrolysis results
in the formation of [Co(enh(eta)]2+ (-35%) and [Co(enh(etaH)OH]2+
(-65%) with kOH = 31 M-
1
S-1 (X = Cl) and kOH = 51 M-
1
S-1 (X = Br)
at I = 1.0 M KN0
3
) and 25C. The product ratio is independent of pH.
The five-coordinate intermediate 15 shown in equation (3) can be attacked
by water or the pendant OH group of the N -coordinated amino-alcohol.
2+
[(en)(en-H) CoNH
2
CH
2
CH
2
0H ]
15
(3)
Oxalato(ammine)(trien)cobalt(III), [Co(trien)(NH
3
)C
2
0
4
H](Cl0
4
h,
and salicylato(ammine)(trien)cobalt(III),
(Cl0
4
h, have been prepared and tentatively assigned a cis-a
configuration. (42) For the oxalato complex kOH = 2.95 X 10-
2
M-
1
S-1
at 30C (MIt = 109 kJ mol-t, = 85 J K-
1
mol-I) at I = 1.0 M. The
salicylato complex follows a more complex rate law with kobs =
kl + kOH[OH-] with kl = 1.58 X 10-
4
S-1 at 30C (Mit = 166 kJ mol-I;
!:J.S
t
= 229 J K-
1
mol-I), and kOH = 3.56 X 10-
3
M-
1
S-1 (Mit =
101 kJ mol-
1
and !:J.S
t
= 42 J K-
1
mol-I). The results are discussed in terms
of an SNICB mechanism involving rate determining Co-O bond cleavage
for both the kl and kOH pathways.
Base hydrolysis of the a{3S -(salicylato )(tetraethylenepentamine)-
cobalt(III) ion (16) has also been investigated. (42) Although the configur-
ation (a{3S or a{3R) has not been fully established it is presumed to be the
H
,/N""
H N I /NH)
2 H

O,c--o
OH
16
a{3S diastereoisomer. The complex a{3S-[Co(tetren)(OCOC
6
H40H)]
CIOh undergoes aquation within the stopped-flow time scale, and base
hydrolysis also occurs much more rapidly than with the trien complexes
discussed above.
Condensation of the deprotonated amine function trans to halide in
the cis-[Co(en)z(NH
2
CH
2
CN)Xf+ ions (X = CI or Br) results in the rapid
formation of the tridentate amidine complex 17.(43) As previously repor-
ted(44) the reaction is first order in both the [complex] and [OH-], The rate

/N?C'CH 2+
/ I / 2
H2N ............ Co /NH2
/1"--.

I
X
17
constants for the ring closure k = 9.6 X 10
3
M-
1
S-1 (X = Cl) and k =
1.5 X 10
4
M-
1
S -1 at 25C and I = 1.0 M (NaCI0
4
) are in good agreement
with the values reported previously(44) at I = 0.1 M, k = 2.6 x 10
4
M-
1
S-1
7.4 Solvolysis 165
(X = Cl) and 4.5 x 10
4
M-
1
S-1 at 25C. Subsequent hydrolysis of halide
from 17 at pH < 13 follows a first-order dependence on [OH-] as previously
noted, but from 0.1 to 1.0M-
1
0H- a discontinuity occurs, owing to
deprotonation of the amidine complex, with both the protonated and
deprotonated species undergoing base hydrolysis. In this pH range kobs is
represented by equation (4) where K is the ionization constant for the
k - k1[OH-] + k2K[OH-]2 (4)
obs - 1 +K[OH ]
amidine complex. For X = CI, kl = 0.88M-
1
s-t, k2 = 0.14M-
1
s-t, and
K = 4.5 M-
1
at 25C and I = 1.0 M. Two products result from both the
k1 and k2 pathways. Product 1 (18) has the same configuration as the
starting complex (with full retention of optical properties), while product
2 (19) has a "planar" configuration of the amidine grouping with inversion
of optical configuration about the metal.
product 1 product 2
18 19
7.4. Solvolysis
The labile complex [Co(NH3h03SF](CI04h has been prepared and
its rate of hydrolysis measured(4S) (k = 2.2 x 10-
2
S-1 in 0.01 M HCI0
4
at 25C). The complex solvolyzes with Co-O bond cleavage to give
[Co(NH
3
h(solvent)]3+ and concurrently with S-F bond cleavage to give
[Co(NH
3
hFf+ and S03 rather than [Co(NH
3
hOS03t + F-. The propor-
tion of [Co(NH3)sFf+ is strongly solvent dependent (H
2
0 or 0.01 M
HCI0
4
, 26%; Me2SO, 44%; 0.01 M NaOH, 0.04%). It is proposed that
the O-bonded [Co(NH3h03SFf+ solvolyzes with Co-O rupture competi-
tively with isomerization to an F-bonded form, which cleaves the S-F bond
to produce [Co(NH
3
hFf+.
The kinetics of solvolysis of [Co(tren)Clzt have been measured in
DMSO, DMF, N -methylformamide (NMF) and formamide. (46) These reac-
tions occur via dissociative mechanisms, and comparisons are made with
the analogous Cr(III) complex. The kinetic data are summarized in Table
Table 7.4. Solvolytic Reactions of [Co(tren)CI
2
J' in Various Solvents (46)
([Co(tren)CI
2
J' + solv -+ [Co(tren)CI(solv)F+ + Cn
104kzsoc
AHt, ASt,
Solvent s
-I
kcal mol-I cal K-
1
mol-I
DMF 0.118 24.6 4.0
DMSO 0.224 21.2 -7
NMF 56.9 17.1 -11.2
Formamide 8.27 20.1 -4.9
7.4. These results give the following values of in cal K-
1
mol-I;
-11.5 (DMSO), -10.2 (DMF), -17.9 (NMF) , and -14.0 (formamide).
Equilibria occur in DMSO and DMF and the concentration of added Cl-
affects both the position of these equilibrium and the rates of solvolysis.
The chloride anation of [Co(tren)CI(DMSO)]2+ was also studied and found
to occur by an (SN 1)IP mechanism. A number of the solvolysis products
have been isolated and characterized. There is evidence that tren may
sterically block nucleophilic attack.
The kinetics of solvolysis of cis-[Co(enhCI(N
3
n+ in water and water-2-
propanol mixtures has also been studied. (47)
7.5. Anation
The kinetics and mechanism of the formation of [Co(NH
3
)sONO]2+
from [Co(NH
3
)sOH
2
]3+ and NO
z
in acidic aqueous solution has been
studied over a range of pH, concentration of NO
z
, temperature, and
pressure. (48) The data favor a mechanism in which [Co(NH
3
)sOH]2+ reacts
with NO+ (from N
2
0
3
) in the rate-determining step. The rate parameters
for this process are k (at 25C) = 7.9 x 10
3
M-
1
s-\ t::J[* =
12.0 kcal mol-I, and = -0.6 cal K-
1
mol-
1
at 30 bar. The results are
discussed with reference to previous work on CO
2
and S02 uptake by
hydroxopentamminecobalt(III).
The kinetics of anation of [Co(NH
3
)sOH
2
]3+ by H
2
PO; /H
3
P0
4
in
aqueous solution have been studied at 50, 60, and 70C and I = 1.0 M
(LiCI0
4
). (49) A rate law of the type kobs = k[H
2
PO;] with little or no
contribution from H
3
P0
4
is observed. No kinetic evidence was obtained
for ion pair formation which occurs in the analogous Cr(lll) system. Values
of k(M-
1
S-l) are 4.5 (50C), 15.4 (60C), and 53.9 (70C), giving t::J[* =
26.9 kcal mol-
1
and = 4.2 cal K-
1
mol-I.
The anation of cis-{3-[Co(trien)(OH
2
h]3+ by H
2
C
2
0
4
, HC
2
0; and
has been studied at 30-45C and I = 1.0 M (KN0
3
). (SO) The com-
mon anation rate constant ko for the two ion pairs {cis-{3-[Co(trien)(OH
2
h],
7.5 Anation 167
H
2
C
2
0
4
} and {cis-{J-[Co(trien)(OH
2
h], HC
2
0
4
} was found to be 6.7 x
lO-
s
s -1 at 40C. The observed anation rate constant levels off to a limiting
value of 7.0 x 10-
3
S-1 at 40C, pH = 4.0 and 0.15 M as a result
of formation of the {cis-{J-[Co(trien)(OH
2
h], ion pair (kl)' Activa-
tion parameters for the ko and kl pathways are tli/* 24.5 kcal mol-t, tlS*
0.8 cal K-
1
mol-I; and tli/* 28.9 kcal mol-t, JiS* 24.0 cal K-
1
mol-t,
respectively. The ion pair constant with H
2
C
2
0
4
is -6.8 M-
1
Anation
within the ion pair is considered to occur by an Id mechanism.
The anation of [Co(tren)(OHht by has been studied in the
pH range 10.5-13 at I = 0.5 M over the temperature range 25-60C.(Sl)
At [OH-] > 0.025 M the rate constant for anation is 4.0 x 10-
4
M-
1
S-1
at 50C with tli/* = 24.2 kcal mol-
1
and tlS* = 1.5 cal K-
1
mol-I. The rate
constant for the reverse reaction (Le., ring opening of [Co(tren)C0
3
t) is
k = 2.8 X 10-
4
S-1 at 50C and pH 13 with tli/* = 25.3 kcal mol-
1
and
tlS* = 3.6 cal K-
1
mol-I. For base hydrolysis of [Co(tren)(OH)(OC0
2
)]
at pH 13 and 50C, k = 3.7 X 1O-
4
s-
1
with tli/* = 23.0kcalmol-
1
and
tlS* = -3.4 cal K-
1
mol-I.
The anation of cis-[Co(enh(OH
2
h]3+ by oxalic acid has been reported
to be catalyzed by nitrate ion. A study of the pressure dependence of plots
of kobs versus the concentration of oxalic acid in both perchlorate and
nitrate media at [H+] = 2.0 M has now been carried OUt.(S2) The reported
data at normal pressure are in good agreement with earlier observations.
The volume of activation for the nitrate-promoted anation process is
interpreted in terms of a dissociative process to give a five-coordinate
intermediate. Discrimination within this intermediate to give the diaquo
or oxalato species is independent of pressure up to 1500 bar.
A series of papers have appeared dealing with anation reactions
involving bidentate ligands. The reaction of cis-[Co(NH
3
MOH
2
h]3+ with
oxalate at pH 1.0 or below was found to occur in a single step. The rate
law is interpreted in terms of an ion-pairing mechanism with an ion-pairing
equilibrium constant of 0.52 M-
1
for H
2
C
2
0
4
and 5.3 M-
1
for HC
2
0
4
.(S3)
This anation reaction was also studied at 73.4C in the presence of added
nitrate ion. (S4) Nitrate ion catalysis is dependent upon the pH of the solution,
and the results are interpreted in terms of the effect of NO;- on ion pair
formation. The anation of by oxalate in the pH
range 3.0-4.0 has also been studied.(SS) The reaction is shown to be rather
complex. At least four reactions appear to be involved in the ultimate
formation of cis-[Co(NH
3
)4(C
2
0
4
)t. The important reactions are the for-
mation of a monodentate oxalato species followed by ring closure to give
the product.
The substitution of [Co(CN)s(OH)]3- by azide ion has been shown to
occur by the reaction of N3 with [Co(CN)s(OH
2
)]2- in equilibrium with
the hydroxo complex.(S6) Deviations from simple second-order rate laws
for the substitution of N
3
, NCS-, and CN- into [Co(CN)s(OH
2
)f- at
I = 1.0 M and 40C are small and can be attributed to variations in ionic
activities. A dissociative mechanism is assigned on the basis of activation
volumes, solvent effects, and nucleophile competition experiments.
Activation volumes for the substitution of diaqua-meso-tetrakis(N-
methyl-4-pyridyl)porphyrinato cobalt(III) by NCS- have been deter-
mined(S7) and provide evidence for the dissociative mechanism shown in
equations (5)-(7).
MPS+X MPSX
MPSX+X MPX
2
+S
(5)
(6)
(7)
The reaction of substituted benzoic acids with cis-[Co(en)zCl(OH
2
)]2+
has been studied and Hammett-type relationships developed.(S8.s9)
7.6. Solvent Exchange, Racemization, Isomerization, and
Ligand Exchange
Solvent-interchange reaction rates have been determined for
[Co(NH
3
)s(NCCH
3
)](Cl0
4
h in acetonitrile-water and in acetonitrile-
DMSO solvent mixtures. (60) Ratios of reactants and products in equilibrium
mixtures and first-order rate constants are reported.
The results indicate that the [Co(NH
3
)s]3+ group in the activated
complex of the Id mechanism for solvent interchange does not undergo
any significant real rotation or pseudo rotation within its solvent cage.
Activation enthalpies for the exchange reactions are summarized in
Table 7.5.
Table 7.5. Activation En tha lpies (601 for the Exchange
Reactions [Co(NH3JsSP+ + L [Co(NH3JsLP+ + S
Complex
[ Co(NH
3
)sNCCH
3
]3+
[Co(NH
3
)sOH
2
r
[Co(NH
3
)s(DMSO)]3+
[Co(NH
3
)sNCCH
3
f+
L
H2 0
CH
3
CN
CH3CN
DMSO
t:..H*,
kcal mol-
1
26.5
28.7
27.0
27.8
7.6 Solvent Exchange, Racemization, Isomerization, Ligand Exchange 169
The synthesis and characterization of trans-[Co(enh(DMSO)C1]-
(CI0
4
h has been described.(61) The rate of isomerization to the cis isomer
has been determined using DMSO as solvent, k
tc
= 1.54 X 10-
3
s -1 at 25C
with !lHt = 105 kJ mol-
1
and !lst = 55 J K-
1
mol-I. The solvent exchange
rate has been measured by IH nmr in (CD
3
hSO at 308.2 K, k
ex
= kit + k
tc
=
7.0 X 10-
3
S-I. The data establish that trans-to-cis isomerization requires
solvent exchange, each act of which leads to substantial rearrangement
(-90% cis at 308.2 K).
Activation parameters for the axial water substitution reactions in the
vitamin B12 model compounds [RCo(dmgHhOH
2
] (R = Me) and
[RCo{(DO)(DOH)pn}OH
2
t (20, R = Me or Et) have been reported.(62)
M
1
' N!f)YMe
""- (0
/1"
N N
Me / H20/He
o ,0
'H""
20
Comparison of the activation parameters with those for the corresponding
reactions of the aquocobalamin suggest that the lability of the biological
complex arises mainly because of entropy effects. The substitution reactions
of aquocobalamin are quite rapid and the rate constants are nearly indepen-
dent of the nature of the incoming ligand. When an alkyl group is present
in the axial position in the cobaloximes and the related complex (20) the
substitution of the water ligand in the trans position is also very rapid and
involves a dissociative mechanism.
Factors influencing ligand exchange reactions in cobaloxime complexes
are discussed in a recent thesis. (63)
+
21
The kinetics of racemization of (+ )s89-[Co(bipyh(paox)]N0
3
(21)
(paox is the dianion of 2-ketopropionic acid oxime) has been studied in
0.1 M NaN03 with 0.05 MpH 7 phosphate buffer over the temperature
range 70-98C.(64) At 98C, k = 4.2 X 10-
6
S-1 with ARt = 22.7 kcal mol-
1
and ASt = -22.6 cal K-
1
mol-I. The reaction is accelerated in the presence
of added bipyridyl, but not by the addition of Co(II). The exchange of
coordinated bipyridine by tritium-labeled bipyridine occurs more rapidly
than racemization, excluding a mechanism involving intramolecular
racemization.
Isotopic exchange of 36Cl in cis-[Co( enhCl(CN) r has been investigated
using methanol and ethylene glycol as the solvent. (65)
7.7. p,-Peroxo-dicobalt(III) Complexes
Peroxo-bridged dicobalt(III) complexes are often regarded as models
for biological oxygen carriers, (66-68) and there has been considerable interest
in the formation and breakdown of such complexes in aqueous solution.
The kinetics of three apparently different reactions of
have been studied(69) in
aqueous solution at 1= 0.1 M (NaCl0
4
) and 15-25C; (a) decomposition
to Co (II) and Oz (pH 1.1-10.2), (b) spontaneous conversion into
[(enhCo(III)(wOH-, (pH 8.4-9.9), and (c) reac-
tion with N02 to give
(enhf+ (pH 8.4-9.8). Rates of all the reactions are almost identical and
are first order in the concentration of the initial complex and are
independent of the concentrations of other species in solution including
[H+], [N0
2
], and [EDTA]. The common first-order rate constant is 4.9 x
10-
3
S-1 at 25C with ARt = 132 kJ mol-
1
and ASt = 151 J K-
1
mol-I. The
common rate-determining step for all three reactions is suggested to be
the decomposition of the initial wperoxo complex to Co(II) and Oz. The
derived complexes should be formed rapidly from the cobalt(II) complexes
and Oz.
The [(Co(cyclam)HzOhOzt+ complex decomposes slowly in acidic
aqueous solution.(70) Solutions of this complex have both oxidiz-
ing and reducing properties. The rates of oxidation and reduction reactions
approach limiting first-order behavior for large concentrations of the
counter-reagent. This behavior is attributed to rate-determining homolytic
dissociation of the complex with the reactive intermediate species
being [Co(cyclam)(OHzh]z+ and [Co(cyclam)(OH
2
)Oz]2+, i.e., the
reverse of the oxygenation reaction (9). It is further suggested that
similar intermediates occur ill the thermal decomposition of
7.8 Formation 171
COL2+ + O
2
(8)
Co(III)LOi + Co(II)L (9)
In acidic chloride solutions the decomposition
products of the J.t-peroxo complex were found to be [Co(cyclam)Cht and
[Co(cyclam)(OH
2
)CIt in about a 1 to 0.8 ratio, a result which suggests
an inner-sphere (CI--bridged) attack of [Co(cyclam)(OH
2
hf+ on

The rate of exchange of 180 in [(tren)(MeNH
2
)Co(J.t_
18
02)Co(tren)-
(MeNH
2
)t+ (22) has been found to be the same as both the rate of

\ NH2
N",' /0-0/ I '--...N
ONH;r'-NH,He H,N--.J

22
decomposition by acids to Co(II) and O
2
and the rate of formation of
[(tren)Co(IL-02,IL-OH)Co(tren)]3+ from 22 in neutral or basic solution.(71)
The results indicate that a cobalt(II) complex is a common intermediate.
The rate of exchange of [(tren)Co(IL-0,IL-OH)Co(tren)]3+ is very much
slower.
7.B. Formation
The rates of the rapid reversible uptake of S02 by [Co(tren)(OH
2
h]3+
have been studied by stopped-flow techniques over the pH range 3.5-6.6
at various temperatures. (72) The kinetic data obtained are summarized in
Table 7.6. Reaction of S02 with [Co(tren)XJ"+ Complexes(72J
klOoC,
Mit
,
I:lst,
Complex s
-I
kcalmol-
I
cal K-
1
mol-I
[Co(tren)(H
2
Ohr 5 x 10
5
36 94
[Co(tren)(H
2
O)(OH)f+ 3.3 x 10
7
4.5 -8
[Co(tren)(OHht 7.6 x 10
8
11.5 23
Table 7.6. Spectral studies show that the product is an O-bonded monoden-
tate sulfito complex, which in the unstable protonated form [Co(tren)-
(OH2)(OS02H)f+ eliminates S02 with the rate parameters of k =
1.4 X 1O-
3
s-
1
(at 10C), llR* = 11.1 kcalmol-t, and llS* =
-4.6 cal K-
1
mol-I. Comparisons are made between the results of this study
and those of previous investigations involving CO
2
, S02, HSeO:3,
HMo0
4
, and HW0
4
.
The rate of S02 uptake by a,8S-[Co(tetren)OHf+ (23) has also been
studied by stopped fiOW.(73) The rate and activation parameters for S02
23
addition are k (10C) = 3.2 x 10
8
M-
1
s-t, llR* = 0.5 kcal mol-t, and
llS* = -21.0 cal K-
1
mol-I. Retardation by and is observed
and is ascribed to the formation of nonreactive ion pairs. The product of
S02 uptake is the O-bonded sulfito complex. At 10C the protonated form
of such a species a,8S-[Co(tetren)OS02H]2+ (pK = 3.3) eliminates S02
with k = 550 s-t, /lH* = 7.2 kcal mol-t, and llS* = -20.4 cal K-
1
mol-I.
The oxygen-bonded sulfito intermediate shows no tendency to undergo
internal redox, but slowly isomerizes to its sulfur-bonded analog.
The complex [Co(tren)(OH
2
)(OS02)t produced via S02 uptake by
the hydroxo-aquo complex undergoes two types of reaction depending
upon the pH of the system.(74) In the pH range 2.9-5.4 an internal redox
process gives cobalt(II) and in an exact stoichiometric ratio, with
k = 1.0 X 10-
3
S-1 at 25C at the high-pH end of the range. Over the pH
range 7.2-8.9, internal redox does not occur, the only observable reaction
being the addition of a second sulfito ligand to give [Co(tren)(S03hf.
Infrared data indicate one O-bonded and one S-bonded sulfito ligand, e.g.,
[Co(tren)(OS02)(S03)f.
Kinetic data on complex formation between [Co(NH
3
)s00C'C0
2
Hf+
and Fe (III) in acidic solution has been reported. (75) Plots of kobs versus
[Fe
3
+]total are linear with pronounced intercepts. The intercepts are essen-
tially independent of [H+] and the slopes decrease with increasing acidity.
A mechanism is proposed in which all possible reactant species are involved
([Fe(H
2
0)6]3+, [Fe(OH)(OH
2
)s]3+, [Co(NH
3
)s00CC0
2
Hf+, and
[Co(NH
3
)s00CC02"t).
7.9 Photochemistry 173
The reaction of meso-tetra(4-N -methylpyridyl)porphinediaquoco-
balt(III), [CoP(H
2
0h]5+ with [CO(CN)6]3-, [Fe(CN)6]3-, [Mo(CN)s]3-, and
[W(CN)S]3- has been studied at 15, 25, and 35Cin 0.1 M H+ atI = 1.00 M
(NaCI0
4
).(76) The formation constants are 446,1320,3100, and 1380M-
1
for [CoP(H
2
0)(anion)]2+, with anion = complexes of Co, Fe, Mo, and W,
respectively. Only one water molecule is displaced during the reactions,
which are first order in the concentration of the complex cyanide. The
second-order rate constants are 0.345, 0.544, 2.54, and 3.73 M-
1
s -1 at
25C for the cyanides of Co, Fe, Mo, and W, respectively. A dissociative
mechanism is suggested.
The reaction of pyridine with meso-tetrakis(p-sulfonatophenyl)por-
phyrinatodiaquocobaltate(III), [Co(TPPS)(H
2
0h]3- has been studied
between pH 2 and 13.(77) A reaction scheme has been developed, and the
various rate constants and activation parameters determined. The kinetic
and equilibrium properties of [Co(TPPS)(H
2
0h]3- are similar to those
observed with other water-soluble cobalt(III)-porphyrin systems.
7.9. Photochemistry
Irradiation of aqueous solutions of [(NC)5CO(JL-NC)Co(NH3h] in
the wavelength region 254-365 nm leads to photoaquation of the
pentacyanocobaltate(III) center to give [Co(CNh(OH
2
)]2- and
[Co(NH
3
hCNf+ with large quantum yields (0.2-0.3 mol einstein-
1
).(78)
These wavelengths represent ligand field excitation of the pentacyanocobal-
tate (III) chromophore. In contrast, ligand field excitation of this
chromophore in the linkage isomer [(NC)sCo(JL-CN)Co(NH
3
)s] leads to
very little reaction at that site. Since [CO(CN)6f- is quite photoactive under
these conditions, the result implies that coordination of the [Co(NH
3
hf+
moiety to one CN provides a new pathway for rapid deactivation of the
[Co(CN)6]3-ligand field states.
The viscosity dependence of the photoaquation of [CO(CN)6]3- has
been studied using glycerol/water mixtures at normal pressure.(79) No
significant cage effect was observed in the photosubstitution of cyanide.
The photoaquation of [CO(CN)6]3- has also been studied as a function of
pressure up to 1500 bar.(SO) The apparent volume of activation, determined
from the pressure dependence of the quantum yield is + 1.3
0.1 cm
3
mol-
1
. A photoaquation mechanism of the Id type is suggested.
Acidopentacyanocobaltate(III) ions exhibit anomalous photochemical
behavior with respect to other Co(III) complexes, in giving photosubstitu-
tion reactions upon ligand to metal charge transfer (LMCT) irradiation.
The charge transfer photochemistry of [Co(CNhOH]3- has now been
investigated in detail. (S1)
Complete ligand replacement of [Co(enh]3+ by bis(2-
hydroxyethyI)dithiocarbamate ion (htc -) forming [Co(htch] is induced by
visible light in aqueous solution. (82) The quantum yield depends on the
wavelength of the light employed and on the concentrations of the complex
and the ligand. A distinctive feature of the photoinduced substitution is
that the quantum yield is > 1 for solution containing 0.02 M [Co(enh]2+
and 0.13 M htc -. This result is rationalized on the basis of a primary
photoredox process followed by a chain reaction involving cobalt(II) species
as chain carriers. Other cobalt(III) complexes with the Co(N
6
)
chromophore, e.g., [Co(NH
3
)6]3+, [Co(NH
3
)4(pn)]3+, [Co(chxnh]3+, and
[Co(dien)]3+ (chxn = 1,2-cyc1ohexanediamine) undergo similar photo-
reactions.
Photodecomposition of cis-[Co(acachN
3
(NH
3
)] occurs with formation
of [Co(acach] and azide radicals.(83) The reaction occurs with radiation
throughout the 250-580-nm region. The results suggest that the photoactive
state is a triplet charge transfer state involving the azide group. The
photo-reaction has an apparent activation energy of 11.7 kcal mol-t, and
solvent assistance in the loss of the azide radical is implicated.
The photochemical formation of [Cl(enhCo-N=C-Fe(CNhf- from
[Co(enh]3+ and [Fe(CN)6]4- has been studied in detail.(84) Racemization
does not accompany the reaction if (+ h89-[Co(enh]3+ is employed as
reactant. The wavelength-dependent photochemistry of a series of sulfur-
and selenium-containing cobalt(III) complexes has been studied. (85) The
complexes are of the [Co(enhLr+ type [L = -SCH
2
CH
2
NH
2
(CoSN),
cysteine-N,S (CoMeSN), S(CH2C6H5)CH2CH2NH2 (CoBzSN),
S(O)CH
2
CH
2
NH
2
, S(OhCH
2
CH
2
NH
2
, -SeCH
2
CH
2
NH
2
(CoSeN), and
-SeCH
2
CO;-]. The photochemical behavior defines three groups: (a) thio
and seleno complexes, which show only photoredox decomposition at all
wavelengths; (b) thioether complexes, for which irradiation in the ligand
field region leads to photoaquation, while irradiation in the charge transfer
region gives both redox decomposition and aquation; and (c) the sulfinato
complex, which shows linkage photoisomerization.
Methylviologen radicals have been generated via the reaction of *My2+
with 2-propanol and the rate constants for the reaction of MY+ with
pentaamminecobalt(III) complexes of pyridine, bipyridine, and their
derivatives measured. (86) Possible mechanisms are considered.
7.10. Reactions of Coordinated Ligands
A considerable volume of interesting work has been published in
this area.
7.10 Reactions of Coordinated Ligands 175
7.10.1. Nitrile Hydrolysis
The base hydrolysis of coordinated acrylonitrile in
[(NH
3
)sCoN=CCH=CH
2
]3+ to give the acrylamide complex has been
studied using carbonate buffers. (87) The reaction obeys the rate law kobs =
kOH[OH-] + (kOH = 35 M-
1
s-t, kc = 1 M-
1
S-l at 25C, and
I = 1.0 M). Tracer studies using
18
0 indicate that the mechanism of hy-
drolysis by involves direct nucleophilic attack at the nitrile group by
with subsequent elimination of CO
2

Coordination of malononitrile, cyanoacetic acid, and ethyl cyanoace-
tate to the [(NH
3
)sCO]3+ group leads to greatly increased acidity of the
methylene protons. Thus the pKa of the coordinated malononitrile in
[(NH
3
hCoNCCH
2
CN]3+ is 5.7 compared with 11.3 for the free ligand at
25C. In basic solution these complexes exist in equilibrium with their
deprotonated species. The protonated complexes are hydrolyzed to coor-
dinated nitriles by both water and hydroxide ion acting as nucleophiles.
The deprotonated complexes undergo intramolecular electron transfer to
give Co (II) and the ligand radical and also act as nucleophiles toward
appropriate substrates (methyl iodide, methyl pyruvate, or bromine) to
give the corresponding substituted species.
Neighboring-group participation in the hydrolysis of coordinated
nitriles has also been studied.(88) The reaction (10) has been studied for
3+
INH
3
)s(oN= (V +
R
(10)
R = H [k
OH
= 1050 M-
1
s-t, aR* = 56.9 kJ mol-t, = 4 J K-
1
mol-
1
at 25C, and I = 1.0 M (LiCI0
4
)] and R = CONH
2
(kOH = 5.8 X
10
6
M-
1
s-t, aR* = 69.1 kJ mol-t, = 184 J K-
1
mol-
1
at 25C). The
unusual kinetic parameters for the latter reaction are attributed to neighbor-
ing-group participation by the amide group (Scheme 1).
7.10.2. Phosphato Complexes
Tracer
18
0 studies have established(89) that base hydrolysis of coordin-
ated acetyl phosphate in the complex [(NH
3
)sCo-OP0
3
COCH
3
t [k
OH
=
0.53 M-
1
S-l at 25C and I = 1.0 M (NaCI0
4
)] occurs by exclusive carbon-
oxygen bond fission. The hydrolysis of the acetyl phenyl phosphate
monoanion is significantly catalyzed by the exchange-inert hydroxo complex
[(NH
3
)sCoOHf+ (k
MOH
= 2.9 X 10-
2
M-
1
S-l at 25C) which operates by
(NH3)s(oN( -0
(=0
1
NH2
3+
o
(NH)
3 S )==I
(=0
1
NH2
Scheme 1
..
fast
a nucleophilic pathway involving attack at the carbonyl carbon. (Other
reactions involving M-OH species are considered in Section 7.10.5.)
The hydrolysis of {3, y-[Co(NH3)4H2P301OJ, in which the triphosphate
ion is coordinated as a bidentate ligand, has been studied(90l in the presence
of [Co(cyclen)(OH)OH
2
f+ (cyclen = 1,4,7,10-tetraazacyclododecane). In
the presence of the macrocyclic complex, the rate of hydrolysis of triphos-
phate to pyrophosphate is increased by a factor of 5 x 10
5
over the rate
for the free ion. The pH rate profile for the reaction indicates that a
deprotonation step with a pK of 7.9 was required for the accelerated
hydrolysis to occur. The results are consistent with the formation of the
binuclear complex 24, followed by internal nucleophilic attack on phos-
phorus by coordinated hydroxide.
o 0 NH3
II II
O-P-O-p -0 I / NH3
/(1 1 ............ (0
(cyclen)Co 0- ? /1 .......... NH3
'OH -O-P-O NH3
II
o
24
Polyphosphates such as pyrophosphate and triphosphate are interest-
ing ligands. Recently the unidentate and bidentate pyrophosphate com-
plexes [Co(NH
3
)sHP
2
0
7
}H
2
0 and [Co(NH3)4HP207}2H20 have been
characterized and their crystal structures determined.(91) The a,p,'}'-triden-
tate[Co(NH
3
h(H
2
P
3
0
lO
)] complex contains two fused six-membered che-
late rings formed by the facial coordination of one 0 from each of the
three phosphate residues.(92) The complex [Co(NH3)4(H2P301O)H20 con-
taining the a,,},-bidentate triphosphate ligand has an eight-membered che-
late ring in a boat conformation stabilized by two interligand H bonds from
the axial ammines above and below the chelate ring to the p- and '}'-
phosphates. (93)
There is considerable scope for much interesting kinetic and mechanis-
tic work on cobalt(III) complexes of phosphate ligands. The early work of
Lincoln and Stranks(94) on the hydrolysis of cis-[Co(en)zP0
4
] in acidic and
basic solution has indicated some of the complexities to be expected in this
area.
7.10.3. Carbinolamine and Imine Formation
The [Co(NH
3
)s(NH
2
CH
2
COCH
3
)]3+ ion undergoes an intramolecular
'base-catalyzed cyclization reaction to give a coordinated carbinolamine,
which undergoes a slower base-catalyzed dehydration to give a chelated
imine. (95) The synthesis, characterization and kinetics of formation of
various reaction products are described. Several reactions of the imine
product have been carried out, including BH4 reduction and condensation
with methyl vinyl ketone.
7.10.4. Coordinated Azides and Nitriles
Organic azides are synthetically very useful reagents. (96) Among the
many and varied transformations which they undergo, one of their most
important are their 1,3-dipolar cycloaddition reactions to produce
heterocycles. (97,98) Several electron-poor dipolarophiles (alkynes, alkenes,
and nitriles) react with azido cobalt complexes of the type [LCo(chelate)N
3
]
under mild conditions. (99) Coordinated five-membered ring heterocycles
are the initial products of these 1,3-dipolar cycloadditions. Nonterminal
alkynes give triazoles, alkenes give triazolines, and nitriles give tetrazoles.
The reactivity of the cobalt complexes is influenced by the nature of the
neutral trans-coordinated ligand L (trans effect) and by the nature of the
anionic chelating ligand (cis effect).
Coordination of organonitriles to the [Co(NH
3
)s]3+ group is known to
enhance the susceptibility of the nitrile carbon to nucleophilic attack by
hydroxide ion and cyanide ion. When aqueous solutions of the complexes
[Co(NH
3
)s(N C-R)]3+ (R = Me or Ph) are treated with an excess of
NaN
3
at pH 5-6 (to prevent base hydrolysis to the amido complex),
significant spectral changes occur attributed to the reactions(100) (Scheme
2).
Scheme 2
N-N
1(-' ,

N
fast '" I ,/
---+ (0
/1''
N
1
-bonded
slow
---+
N2 -bonded
The formation of 5-methyltetrazole from sodium azide and acetonitrile
requires a reaction time of 25 h at 150C(10l) compared with only 2 h at
ambient temperature for coordinated acetonitrile.
The subsequent conversion of the N I-bonded complex to an Nz-bonded
complex has been verified as the latter complex has been prepared and its
crystal structure determined. (102)
7.10.5. Cobalt-Hydroxide-Promoted Hydrolysis and Lactonization
The possibility that coordinated hydroxide is directly involved in the
catalytic action of some metalloenzymes such as carbonic anhydrase has
prompted a number of investigations of metal hydroxide reactivity towards
organic substrates. The [Co(NH
3
)sOHf+ (and other exchange-labile and
7.10 Reactions of Coordinated Ligands
179
non labile metal hydroxide species) promoted hydrolysis of 2,4-dinitro-
phenyl acetate and 4-nitrophenyl acetate has been studied in some
detail. (103) Kinetic studies (25C, I = 1.0 M) show that these reactions
follow shallow slopes ({3 0.33 and 0.40 for the two substrates)
which extend over a range of 10lD in nucleophile basicity. A correlation is
reported which allows the prediction of reaction rates between
[Co(NH
3
)sOHf+ and other activated charge neutral carbonyl substrates
such as CO
2
and propionic anhydride.
The [Co([15]aneN
s
)OHf+ -promoted hydrolysis of 4-nitrophenyl
acetate has also been investigated in some detail(104) ([15]aneN
s
=
1,4,7, 10, 13-penta-azacyclopentadecane). This complex has the structure
25. The pKa for the aquo hydroxo equilibrium is 6.3 at 25C, not
H
2+

N",
[NH
HN
J
("-c ..........
N"""""'- l'----NH
NH HN
H--':'--
LJ
I
OH
[15] aneN
s
2S
markedly different from that of [Co(NH
3
)sOH]2+ where pKa = 6.4. For
the macrocyclic complex 25 k
MOH
= 9.3 X 10-
3
M-
1
S-l at 25C and I =
0.1 M. In absolute terms the macro cyclic complex is some six times more
reactive towards 4-nitrophenyl acetate than [(NH3)SCoOH]2+, where
k
MOH
= 1.52 X 10-
3
M-
1
S-l at 25C.
Tracer studies using 180 have shown that cyclization of cis-
[Co(en)z(OH
2
)(glyOH)]3+ and cis-[Co(en)z(OH
2
)(glyO)]2+ (glyOH =
N-bound NH
2
CH
2
C0
2
H; glyO = N-bound NH
2
CH
2
C0
2
) to give
[Co(enh(glyO)]2+ (26) containing chelated glycinate occur intramolecularly
without displacement of coordinated water. (lOS) The rates of these reactions
2+
26
180 7. S,lbstitution Reactions-Coordination Nos. 6 and Above: Cobalt
are relatively fast with t1/2 - 40 s at pH 0-1 and t1/2 - 400 s at pH 4. Ring
closure of cis-[Co(en)z(OH
2
)(glyO)]2+ is catalyzed by general acids (includ-
ing H30+) and is interpreted in terms of rate-determining protonation of
an intermediate cyclic species. Interestingly cyclization of cis-
[Co(en)z(OH)(glyO)t shown in equation (11) is considerably slower
2+
OH CO.
en I 2
2"
NH _CH2
2
k
-+ + OW (11)
(tl/2 - 10 h) and is not catalyzed by monofunctional buffers. Comparisons
with 0 exchange in glycine indicate large rate accelerations for the metal-
based system (10
7
_1012 M), and the rates compare favorably with those
found for intramolecular lactone formation in purely organic molecules.
Formation of [Co(en)zglyO)f+ from monodentate trans-
[Co(enh(H
2
0jOH)(glyOjH)]3+/2+1+ species has also been studied.(106)
The results support a process involving the synergic of coor-
dinated water or hydroxide by the trans-carboxylic acid or carboxylic anion
(Scheme 3). Tracer studies e
8
0) clearly eliminate any prior isomerization
to, or equilibration with, the cis-aquo ions.
NH
2
CH
2
CO
z
H
I
trans - (en)Co (en)
- I
OH
2
(OH)
Scheme 3
---'"

HzC-- C=--O(H)
I Ii
H2N 0'
'\/
(en)Co(en)
/
./ NHz-CH
z
( ) C
./ (+H +)
en z 0.......... I
O-C
- -
'0
Scheme 4
-
7.10.6. Peptide Synthesis
The rapid aminolysis of cobalt(III)-chelated glycine esters in apr otic
solvents has previously been described,(107-109) [Scheme 4; N4 = (enh or
trien, R = Me, Et, R' = H, CHR"C0
2
Et] and it was suggested that the
reaction could prove useful for peptide synthesis. The cobalt atom acts as
both an N-protonating and activating group. The synthesis of the chelated
amino acid esters has presented some difficulties.(llO) A recent paper(lll)
describes the use of methyl trifluoromethane sulfonate for the alkylation
of chelated amino acids using dry trimethyl phosphate as solvent (Scheme
5). The cobalt(III) amino acid methyl esters are readily isolated as orange
powders following trituration with Et
2
0jMeOH. Some have been recrys-
tallized from MeOH as CIO; or r salts. Their coupling is rapid in dry
DMSO, acetonitrile, or methanol.
Scheme 5
3+
The [Co(enh] and [Co(trien)] moieties are chiral and some specificity
is induced when optically active cobalt(III) units are employed.
Kinetic studies in acetonitrile show that coupling to a- and A-
[Co(enh(AA-OMe)](CF
3
S0
3
h follows overall second-order kinetics with
specific rate ratios k/l./kt.. of 2.7, 1.0,2.0, and 1.5 for the combinations
CoAA-OMe: AA-OEt = Ala: Phe, Phe: Phe, Val: Phe, and Ala: Val,
respectively. By choosing the appropriate cobalt(III) chirality some control
can be exercised in avoiding couplings to mutarotated amino acid residues.
The syntheses of tetrapeptides and [leus]enkephalin by the cobalt(III)
technique has been described,(112) and the method now provides a com-
pletely viable method for peptide synthesis.
7.10.7. Dimethylglyoxime Complexes and BI2 Models
The proton transfer reactions of bis(dimethylglyoximato)cobalt(III)
complexes [Co(III)(dmgHhX
2
r+ (X = NH3 or CN) with OH- have been
studied in dioxane-water media by temperature jump techniquesY
13
) The
rate constant, kf> for the direct proton transfer from [Co(III)(dmgHhX
2
r+
to OH- was found to be 1.6 x 10s-2.9 x 10
6
M-
1
S-1 in aqueous solution.
The effect of the dioxane constant has been studied in detail.
The effect of axial ligands on the base-catalyzed cleavage of
ethylcobaloxime has been investigated kinetically. (114) The ratio of ethy-
lene/ethane produced at 50C and 1.0M KOH is a function of the
concentration of added pyridine.
Sterically hindered secondary alkylcobalamins carrying hydrogen in
the {3 position decompose spontaneously in neutral aqueous solution by a
(3-elimination processYlS) The cleavage of the Co-C bond in these com-
pounds is caused by "upward" distortions of the corrin ligand in response
to the attachment of the axial base, 5,6-dimethylbenzimidazole, as well as
by thermal motions of the corrin ring system. Further insight into the
mechanism of Co-C bond cleavage is provided by the activation parameters
(Mit, I1S
t
, and I1G
t
) for Co-C bond thermolysis is neopentyl, benzyl,
isopropyl, and isobutylcorrins. From the Mit values the Co-C bond dissoci-
ation energies of these organocorrins are estimated to range between 20
and 32 kcal mol-I.
The reaction between methylcobalamin and metal compounds plays
a major role in biological transmethylation and may also be involved in
the geochemical cycling of metals. The kinetics and mechanism of this
reaction have been reported in detail for mercury(II) salts, [PdCI
4
f-, and
chloroplatinum(IV) compounds. The effect of the chloride ion concentra-
tion on the reaction of Hg(OAch with CH3B12 has now been investigated
in detail.(116) The reaction rate decreases markedly as the [Cn/[Hg(II)]total
ratio is increased.
A series of complexes of the type [(n-Bu
3
P)Co(dmgHh(5-R-tetrazo-
late)] [R = CF
3
, CH
3
, C
6
H
s
, C
6
H
s
CH
2
, (CH
3
hN, 4-FCsH4' or 3-FC6H4]
have been treated with a variety of alkylating agentsY17) Nuclear magnetic
7.10 Reactions of Coordinated Ligands
183
resonance spectral comparisons with known compounds indicated that in
each case regiospecific alkylation of the coordinated tetrazolate produced
exclusively 1,5-disubstituted tetrazoles. Long-lived intermediates were
observed spectroscopically in the alkylations of the 5-methyl- and 5-
benzyltetrazolate complexes. The rate constants and activation parameters
are consistent with an overall second-order nucleophilic attack of the alkyl
halide on the coordinated tetrazolate to form an intimately associated
charged intermediate. Formation of the intermediate is followed by a
dissociative interchange of halide and 1,5-disubstituted tetrazole producing
[(n-Bu3P)Co(dmgHhX] and liberating free 1,5-disubstituted tetrazole.
Few transition-metal-alkyl bond dissociation energies have been
reliably determined, owing in large part to the limited applicability of
the methods of determination currently available. The thermal decomposi-
tion of certain organocobalt compounds proceeds by homolytic cobalt-
carbon bond dissociation and bond dissociation energies can be obtained
from kinetic measurements. Interest in such investigations is enhanced by
the relevance of organocobalt compounds as coenzyme B12 analogs. Hal-
pern and coworkers(118) have studied the thermal decomposition of
organocobalt Schiff base compounds [py(saloph)Co-R] [py = pyridine,
[eoIII-R]

[Call] + A
Scheme 6
[eo II] + R.

A + x ( x2 )
Table 7.7. Thermal Decomposition of [py(saloph)Co-R] in Pyridine Solution
Containing n-C
B
H
17
SH(llB)
kl (70C),
t:.Ht, t:.st,
DCo- R,
a
R
-1
kcal mol-
1
cal K-
1
mol-
1
kcal mol-
1
s
CH
2
CH
2
CH
3
4.7 X 10-
4
27.1 2.6 25
CH(CH
3
h
5.7 x 10-
2
21.8 -2.9 20
CH2C(CH3h
3.4 x 10-
2
20.3 -6.2 18
CH
2
C
6
H
s
1.2 x 10-
2
23.6 1.3 22
a D
Co
_
R
- (!:J.H
t
- 2) kcal mo]-'.
saloph = N,N'-bis(salicylidene)-o-phenylenediamine and R = alkyl or ben-
zyl] which proceed readily in pyridine solution below lOOC (Scheme 6)
in the presence of an efficient radical trap n-CgH17SH (= XH). The kinetic
data are summarized in Table 7.7, giving values of D
Co
-
R
in the range
18-25 kcal mol-I. The results support the view that steric factors play an
important role in promoting the bond heterolysis.
The trans-dimethylcobalt(III) complexes [(CH
3
hCo(chel)] (27) and
[(CH
3
hCo(TIM)]Cl04 'H
2
0 (28) rapidly transfer methyl groups to Zn(II)
H
0/ ""0
I Me I
yN,I/N::(

[(CH
3
),Co(chel)]
27 28
and Cd(II) in acetonitrile.(119) IH nmr studies demonstrate the presence of
organozinc or organocadmium intermediates in acetonitrile. The CH
3
Zn +
or CH
3
Cd+ product in the 1 : 1 reaction slowly evolves methane, but only
CH
3
Zn + does so by pseudo-fIrst-order kinetics. Reactions of excess dimethyl
complex with Zn(II) or Cd (II) form the transient intermediates (CH
3
hZn
and (CH
3
hCd, which rapidly evolve methane via solvolysis reactions.
[CH
3
CoL] is always produced from the cobalt reagent.
7.10.B. Base-Catalyzed Exchange Reactions
The activation of methyl groups in coordination compounds has been
recognized for some time. The methyl hydrogens of a variety of (3-
diketonato complexes of the type 29 [N4 = (NH3)4, (enh, (pnh, (bpYh,
2+
/Me
0-(
N
(
/ ---<'(-Ii
4 0 '/
'-.... ---
0--(
'R
29
and R = CH
3
or CF
3
] have been found to undergo base-catalyzed deuter-
ation in deuterium oxide, (120) Table 7.8. It is noteworthy that the rate of
exchange of [Co(bpyh(acac)]Br2 is about three orders of magnitude larger
than the rates of the (NH
3
)4, (enh, and (pnh complexes and is also much
larger than that for a-hydrogen exchange in [Co(enh(gly)]2+.
Table 7.8. Rates of Methyl Hydrogen Exchange
at 36.4C (Ref. 120)
Complex
[Co(NH
3
)4(acac)]!z
[Co(en)z(acac)]I
2
[Co(pn)z(acac)]h
[Co(bpyh(acac)]Br2
[Co(phen)z(acac)]Br2
[Co(en)z(tfac)]I
2
[Co(pn)z(tfac)]I2
2.9 X 10-
3
3.7 X 10-
3
5.0 X 10-
3
1.9
Decomposition
5.5 x 10
5.5 x 10
Under mildly basic conditions complexes such as [Co(enh(gly)]2+ react
with simple aldehydes; thus acetaldehyde gives rise to threonine and allo-
threonine [equation (12)] in proportions depending on the pH of the
2.
2
(12)
solution. The preparation and characterization of N -arylmethylgly-
cinatobis(ethylenediamine)cobalt(III) complexes has been described(121)
(aryl = phenyl, 2-methylphenyl, and naphthyl). The exchange of the
diastereotopic glycinate methylene protons proceeds stereoselectively in
the phenyl derivative but nonstereoselectively in the other two compounds.
The lH and 13C nmr spectra of [Co(NH
3
)s(ImH)]3+ and the lH nmr
spectra of cis-a-[Co(trien)(ImHh]3+ and cis-a-[Co(trien)(ImHh]3+ have
been recorded(122) (ImH = imidazole). The pKa values of coordinated
imidazole determined from the dependence of the chemical shift on pH
are 10.0,9.6, and 10.1, respectively. The C-2 proton is not exchanged with
solvent deuterium under acidic or basic conditions, in marked contrast to
the rapid exchange observed in free imidazole and I-methyl imidazole.
Lack of C-2 exchange should be useful for the identification of metal-
coordinated histidines in proteins.
Chapter 8
and Above: Other Inert
Centers
In this chapter we deal with such standard inert centers as rhodium(III),
iridium(III), and low-spin iron(II), and also with several centers of inter-
mediate lability which are related, or which fall uneasily into the general
classification system of this volume.
8.1. Groups V to VII
8.1.1. Vanadium
Rate laws, rate constants, and activation parameters have been estab-
lished for exchange of acetyl acetone (acacH) with [V(acachJ in several
organic solvents, including acetyl acetone itself. The mechanism is thought
to be associative, but to involve intermediates containing unidentate acetyl-
acetonate. Rate constants for exchange in methanol, ethanol, chloroform,
acetonitrile, and dimethyl sulfoxide cover a range of 10
3
; rates appear to
187
188 8 Substitution Reactions-Nos. 6 and Above: Other Inert Centers
be primarily determined by solvent acceptor numbers, AN. (1) An associative
mechanism is also thought to operate for exchange of malonate with
[V(malh]3-, and for the reactions of this complex with ethylene-
diaminetetraacetate and with nitrilotriacetate. (2)
8.1.2. Molybdenum
Many details have been unraveled in the reaction sequence by
which ammonia is generated from the halogeno-molybdenum(IV) cations
trans-[Mo(NH)X(dppeht, where X == F, CI, Br, or I, and dppe ==
Ph
2
PCH
2
CH
2
PPh
2
, on treatment with base. These cationic complexes are
inert in acidic methanol, but react with methoxide in methanol. The
methoxide deprotonates the NH ligand; the nitrido ligand thus generated
renders trans -chloride, bromide, or iodide labile. The common intermediate
resulting from halide loss, [MoN(dppeht, reacts further with methoxide
and abstracts a proton from the solvent to give [Mo(NH)(OMe)(dppeh],
which gives ammonia with concomitant chelate ring opening. Kinetic par-
ameters are given for this last step. Interestingly, the stronger molybdenum-
fluoride bond in trans-[Mo(NH)F(dppeht results in rate-determining
Mo-F bond breaking in the case of this complexY) The temperature
dependence of nmr spectra of solutions of [MoS
2
(EhNOh] and of the
R2N,
0, I/o

0 .... 1 ............ 0
RN/
2
1
compound 1 (R == Et or Bz) cannot be ascribed simply to inversion at
nitrogen, but to rotation-inversion in an intermediate generated in rate-
determining molybdenum-nitrogen bond breaking. Coalescence tem-
peratures and Gibbs free energy of activation barriers are given. (4)
8.1.3. Tungsten
Mechanisms of substitution at [WF
6
] by various anionic nucleophiles,
in particular azide and cyanide, have been investigated. Kinetic parameters
have been obtained for [WF
6
N
3
r and [WF
6
CNr, in liquid sulfur dioxide.
Exchange takes place by an associative mechanism.(S) A dissociative
mechanism seems improbable in the light of thermochemical information
(fflHt)(6) on the previously characterized(7) compound [WF
s
N
3
].(S)
8.1 Groups V to VII 189
8.1.4. Manganese
Both six- and five-coordinate species are involved in {3 -diketone
exchange reactions of manganese (III)-chloride-{3 -diketone complexes.
Kinetic data have been obtained in dichloromethane solution; the starting
complex contains five-coordinate manganese in this solvent, but six-coor-
dinate in donor solvents. (S)
8.1.5. Technetium
The continuing development of technetium complexes for radiophar-
maceutical use is reflected in a large number of publications in this field.
There are very few thorough investigations of kinetics and mechanisms of
reactions of technetium compounds, but a number of investigations have
yielded qualitative indications of reactivity or of mechanism. Many papers
in the latter class are mentioned here; it is to be hoped that their kinetic
and mechanistic aspects will be properly developed in the near future.
The reaction of the technetium(V)-gluconate complex [TcO(gluchr
with unithiol (2,3-dimercaptopropane sulfonate, HSCH
2
CH(SH)CH
2
S0
3
)
takes place in two kinetically distinct steps. This pattern parallels that
reported earlier for the reaction of bis(citrato)-oxotechnetate(V) with cys-
teine, but differs from the one-step kinetic pattern reported for reaction
of bis(gluconato)oxotechnetate(V) with dimercaptosuccinate(dmsa).(9} The
dependence of rate constants on pH and on concentrations of added citrate
or diethylenetriaminepentaacetate (dtpa) has been established for displace-
ment of citrate and of dtpa from their respective technetium complexes by
transferrin yO} Ligand substitution in oxotechnetium(V) complexes with a
TcON
2
S
2
core is also slow/
ll
} but reaction of [TcOCI
4
r with penicillamine
is very rapid.(12}
Technetium complexes with dtpa, dmsa, or mdp (methylene diphos-
phonate) can be prepared by exchange reactions of the respective rhenium
complexes with pertechnetateY3} Despite the complication that redox as
well as substitution is involved here, rates correlate with metal-ligand bond
strengths. A detailed kinetic study of these reactions would be welcome.
Another type of ligand exchange reaction where kinetic studies are needed
is the similar situation encountered in the preparation of technetium(III),
(IV), or (V) complexes by reduction of pertechnetate with tin (II) complexes
of the respective ligands.
Photochemical aquation of hexachlorotechnetate(IV) has been
reviewedY4} Chloride substitution by thiocyanate, to give [Tc(NCS)6]2-, is
very slowY
S
} The dinuclear anion [Tc2C1s]3- undergoes substitution by
acetate,(16} as by pivalate,(17} only slowly. Although [Tc
2
CI
s
f- is very
susceptible to oxidation to [Tc2Cls]3-, in the absence of oxygen it dispropor-
tionates very slowlyY
S
) The acetylacetonate complex of technetium(III),
[Tc(acach], is also inert to substitution. (19)
It has recently been demonstrated, by
17
0 and 99Tc nmr spectros-
(2021) h T 0- . d . h h
copy, . ,t at c 4 IS, as expecte ,mert to oxygen exc ange on t e nmr
time scale. The
17
0 nmr spectrum shows the ten lines corresponding to
coupling with 99Tc (S = 9/2) in the slow exchange limit. (20) Such ligands
as cysteine, unithiol, benzenethiols, and dmsa react with pertechnetate to
give complexes of technetium(IV) or (V). These reactions are slow, proceed-
ing by rate-determining attack of the ligand at HTc04 with subsequent
more rapid reduction. The activation parameters for the reaction with dmsa
are t:..Ht = 13 kcal mol-
1
and t:..st = 22 cal deg-
1
mol-
1
.(22) Although per-
tech net ate is reduced slowly by concentrated hydrochloric or hydrobromic
acids, such reduction is slow enough to permit the preparation of the
technetium(VII) species [TC03X(LL)] by reaction of pertechnetate with
ligands LL (2,2'-bipyridyl or 1,10-phenanthroline) in these concentrated
hydrohalic acids. (23) Reaction of pertechnetate with pyridoxal and gluta-
mate is very slow, but whether the rate-determining step is attack at
technetium(VII), reduction, or condensation of the organic species to give
pyridoxylideneglutamate (on or off the technetium) has not been estab-
lished. (24)
8.1.6. Rhenium
Some mechanistic speculation has been offered for reactions of trans-
[ReOX
3
(PPh
3
h], X = CI or Br, with Schiff bases of the substituted salicyl-
ideneimine type on the basis of preparative and spectroscopic data. (2S) The
first step in the reactions of the rhenium(V) products of these reactions
with dimethylphenylphosphine to give rhenium(III) species is simple dis-
placement of PPh
3
by PMe
2
Ph. (26) Zirconium(IV) catalysis of substitution
at the [ReF
6
]2- anion, containing inert d
3
rhenium(IV), is mentioned under
osmium(IV) below.
8.2. Iron
8.2.1. Pentacyanoferrates(II)
Dissolution of the sodium salts of the [Fe(CN)s(NH
3
)]3- or
[Fe(CN)s(S03)]s- anions gives the aquo ion [Fe(CN)s(OH
2
)]3- and its
dimer. For the ammine complex in acidic solution the rate-determining
step is dimerization, for which the rate constant is 1.1 dm
3
mol-
1
S-1 at
298 K, but in alkaline or neutral solution the rate-determining step is
8.2 Iron 191
reaction of the [Fe(CN)s(OH
2
)]3- produced with another [Fe(CN)s(NH
3
)]3-
ion. For the sulfite complex aquation is rate determining, with the limiting
rate constant (D mechanism) 5.7 x 10-
5
S -1 at 298 K and an ionic strength
of 1 mol dm-
3
.(27)
The kinetics of dissociation and of formation of the pentacyanofer-
rate(II) complexes of cysteine, penicillamine, glutathione, and 2-mercapto-
ethylamine have been established; pyrazine was used as incoming ligand
in the dissociation studies. The pH dependence of both dissociation and
formation can be ascribed to protonation equilibria of the ligands. (28)
Kinetics both of dissociation and of formation have also been studied for
the 2-methyl pyrazine complex [Fe(CN)s(2Mepz)]3-, 2. Dissociation was
Me 3-
1
2
induced by laser; the kinetic investigation concentrated on the subsequent
recombination reaction, carried out in the presence of an excess of 2-methyl
pyrazine. Two intermediates, 3 and 4, were of kinetic significance en route
1
3-
3 4
to the product, 2. The aquo species 3 reacts with 2-methyl pyrazine with
a rate constant of 475 dm
3
mol-
1
s -1 at 298 K, within the normal range for
formation reactions of the [Fe(CN)sOH
2
)]3- anion; activation parameters
are t1.H* = 16.0 kcal mol-
1
and t1.S* = 7.7 cal deg-
1
mol-I. The kinetics of
isomerization of 4 to 2 indicate two parallel processes, one dissociative
and one associative in character.(29) A controversy over the kinetics of
reaction of [Fe(CN)s(OH
2
)]3- with thiourea and their interpretation was
chronicled in Volume 1 of this series; further results and discussion have
now appeared. (30)
Given a suitable potential bridging ligand (Y), such as 4,4' -bipyridyl,
4-cyanopyridine, or pyrazine, metal complexes can be used as ligands for
pentacyanoferrate(II) as in equation (1). The value of k
f
is about a thousand
(1)
times larger for MLs = Rh(NH
3
)s than for MLs = Co(CN)s, a difference
readily attributable to electrostatics. The values of kb are very similar for
these two MLs moieties.(31)
A study of photochemical aspects of the nitroprusside anion in relation
to its use in pharmacy gives some kinetic information, including the pH
dependence of rates. (32)
The reaction of hexacyanoferrate(II) with 2,2' -bipyridyl in the presence
of mercury(II) gives [Fe(bipyhf+ or [Fe(bipy)(CN)4f- depending on the
relative amounts of reagents. (33) Rate laws, rate constants, and activation
parameters have been established for the two cases of excess of 2,2'-
bipyridyl and excess of mercury(II). Mechanisms for these two paths are
proposed, involving both 1: 1 and 2: 1 Hg2+: [Fe(CN)6J
4
- adducts as
kinetically significant intermediates. (34)
8.2.2. Iron(II)-Diimine Complexes
Several papers report effects of added salts, micelles, and solvents on
rates of racemization and dissociation of the tris (l,lO-phenanthroline)-
iron(II) cation, [Fe(phenhf+, and closely related complexes. Rate con-
stants for aquation of [Fe(phenhJ
2
+ decrease as the concentration of added
chlorides or bromides of the alkali metals, the alkaline earths, or ammonium
is increased. Bromides have a greater effect than chlorides, 2+ cations have
a larger effect than 1 + cations, and small cations have a larger effect than
large. All these trends are attributed to the removal of water from bulk
solvent by incorporation into ion hydration shells. Support for this comes
from correlation with such parameters as single-ion hydration enthalpies.
Deviations from linearity in plots of rate constants against added salt
concentration are ascribed to ion pair formation and ill-defined
"nucleophilic action".(3S) A slightly more complicated pattern is emerging
for salt effects on aquation of the [Fe(bipyhf+ cation.(36) Vague discussion
of nucleophilic attack by added anions also appears in a report of the effects
of added salts, and of pyridine and thiourea, on [Fe(phenhf+ aquation
and racemization. Different ordering of effects on these two processes is
explained by the dominance of u-donor properties in the case of aquation,
of polarizability in the case of racemization. (37) Comprehension of this
paper is hindered by the authors' apparent lack of cognizance of the fact
that their added anions span the wide range from cyanide, which reacts as
a genuine and strong nucleophile, through such anions as azide and fluoride,
over whose nucleophilic powers in relation to iron(II)-diimine complexes
opinions have for many years differed, to anions which could not conceiv-
ably act as nucleophiles. It is difficult to accept the common interchange
8.2 Iron 193
mechanism, apparently involving significant anion-metal interaction, for
the whole range of systems covered.
/\. the effects of a variety of added
cations on aquation and racemization of [Fe(phenh]2+. Alkali metal
bromides have no significant effect on racemization rates, but decrease
aquation rates. Tetraalkylammonium bromides increase racemization rates
by factors of up to about three times, and decrease aquation rates by up
to a half. Salts, [RMe3N]Br, where R is a long-chain alkyl group, have
more marked effects. Hydrophobic aggregation effects are discussed, and
various interaction constants derived.(38) There is much mathematical treat-
ment of the results, but only superficial chemical consideration of the
reactivity trends, especially of the differences between aquation and
racemization patterns. There is also, in contrast to an earlier and much
more restricted study, no real attempt to establish whether the observed
effects can be attributed to initial state or transition state contribution, or
to both. Aggregate formation is also important in determining rates of
aquation and racemization of [Fe(phenhr+ in the presence of sodium
alkanesulfonates; aggregation rather than micellar catalysis is involved
here.(39) However, addition of the newly prepared surfactant dodecyl-
pyrazinium chloride does increase the rate of aquation of [Fe(phenhr+ by
micellar catalysis. Favorable hydrophobic interactions assist the dissociation
of the 1,lO-phenanthroline ligand.(40)
i
H
-
CH
Me- N 'N-Me
5
Rate constants for racemization of the [Fe(gmihr+ cation, where gmi
is the simple aliphatic diimine ligand 5, in a range of solvents increase in
the order
water < nitro methane < formamide < dimethyl sulfoxide
This order parallels that established for the [Fe(bipyhr+ and [Fe(phenhr+
cations. Rates for the gmi complex are, however, less sensitive to solvent
variation than those for the bipy and phen complexes. (41) A theoretical
treatment of racemization of low-spin iron(II) diimine complexes leads to
the conclusion that spin change must occur at some stage. It seems that in
racemization, isomerization, and dissociation of complexes of this type it
is energetically less unfavorable to disobey spin selection rules than Wood-
ward-Hoffmann rules. (42) This suggestion of such spin change in these
reactions is not unique, (43) but this seems to be the first thorough theoretical
treatment. The more likely spin change is to the lowest quintet state C T
2
); (42)
here and elsewhere(44) triplet state species are implausible. A spin change,
which would perforce be accompanied by a lengthening of iron-nitrogen
distances, is also consistent with the markedly positive activation volumes
established(43) for aquation of [Fe(bipyh]2+ and [Fe(phenhf+. Activation
volumes here are very different from those reported for analogous reactions
of nickel(II) and chromium(III) complexes, where no spin change is likely
to be involved. There is only a very small deuterium isotope effect on
activation volumes for aquation of [Fe(bipyh]2+ in acid solution. In molar
acid values are a vt = 12.3, a vb = 13.3 cm
3
mol-
1
.(43)
Before leaving the question of magnetic moments in reactions of
iron(II)-diimine complexes it is necessary to mention the strange case of
complexes of the Schiff base ligand 6, sb. Many years ago the tris(ligand)
() {N-{ )
6
complex was prepared, found to be diamagnetic, to undergo substitution
slowly, and to have the charge transfer spectrum characteristic of low-spin
iron(II) complexes with heteroaromatic ligands.(45) Now it is claimed that
[Fe(sb h](NCSh contains an octahedral but high-spin [Fe(sb h]2+ cation. (46)
Moreover, although the method of preparation could (quantities are not
specified) conceivably give [Fe(sbh(NCSh], which could well be high spin,
in fact this complex is also described in the paper in question. (46)
Kinetics of aquation, base hydrolysis, cyanide attack, and peroxodisul-
fate oxidation have been investigated for the 4-methyl-1, 10-phenanthroline
complex [Fe(4Me phenhf+.* The main interest here is that another
demonstration is provided of the dominant role of solvation changes in
determining activation volumes when heavily solvated ions, such as cyanide
here, are involved. The minimal change in a v* on going from water as
solvent to 33% methanol is also ascribable to heavy and strongly preferen-
tial hydration of the cyanide. (47) In a similar vein, the zero activation volume
for peroxodisulfate oxidation of the [Fe(bipy)(CN)4]2- anion, surely simple
bimolecular outer-sphere electron transfer, can also be explained by balanc-
* There was no indication of the presence of two isomers in this case. However, the detection
of mer- and fac- isomers has recently been described for the tris (4-methyl-1,10-phenanthro-
line) and tris (4-methyl-2,2'-bipyridyI) complexes of ruthenium(II) [M. J. Cook, A. P.
Lewis, G. S. G. McAuliffe, and A. J. Thompson, [narg. Chim. Acta 64, L25 (1982)]. The
possibility of the presence of both isomers should always be borne in mind in kinetic studies
of tris-unsymmetrical diimine complexes, as indeed was shown many years ago in relation
to Schiff base complexes of iron(II) [Po Krumholz, [narg. Chem. 4, 609 (1965)].
8.2 Iron 195
ing hydration changes against the intrinsic volume decrease for a
bimolecular process. (48) Recent calorimetric studies on the association
between peroxodisulfate and metal ions in aqueous solution provide sup-
porting evidence on the role of hydration changes in peroxodisulfate oxida-
tion activation volumes. (49)
Solvation changes for the initial and transition states of several reac-
tions of phen and bipy complexes in binary aqueous mixtures have been
assessed, qualitatively and semiquantitatively, from kinetic and thermo-
dynamic (solubility) data. (50) The small decrease in the rate constant for
dissociation of [Fe(bipyh(CNhJ in aqueous ethanol as the proportion of
ethanol increases can confidently be assigned to rather greater stabilization
of the initial state than of the transition state (Figure 8.1). Conversely, the
slight increase in aquation rate for the [Fe(phenhJ
2
+ cation as methanol
or acetone is added to an aqueous solution can be assigned to slightly
greater stabilization of the transition state than of the initial state. But
addition of acetonitrile parallels the [Fe(bipy)z(CN)ZJ pattern. Conclusions
+
om P, ...
kJ mot-
1
-2
-4
Figure 8.1. Two representations of the initial state and transition state contributions to the
decrease in rate (increase in Gibbs free energy of activation, for the dissociation of
[Fe(bipyh(CNhl on going from water to aqueous ethanol.
for the [Fe(phenh]2+ cation, as for any charged species, must be viewed
with a certain degree of caution, of course, as they unavoidably involve
extrathermodynamic assumptions in obtaining the required single-ion
transfer parameters. Difficulties associated with this are clear in the attempt
to extend the earlier initial state-transition state analysis of reactivity trends
with solvent composition for the reaction of [Fe(bipyhf+ with cyanide(51)
to include the final state. This, being [Fe(bipy)z(CN)z], does not cause a
problem, but relating this to the reactants and transition state is complicated
by the assumptions needed for these. The molybdenum(O) (also d
6
low-
spin) compound [Mo(COMbipy)] is another uncharged compound of use
in this connection. (52)
The detailed mechanism of attack of nucleophiles at diimine com-
plexes, in particular the operation or otherwise of Gillard's much discussed
initial attack at a carbon atom of the coordinated ligand, continues to
attract interest. Further studies of hydroxide and of cyanide attack at the
[Fe(fzht- anion (fz = the ligand 7) in binary aqueous solvent mixtures,
S03-
<: > ,N-;,
N N-N
7
and in the presence of cationic micellar agents, provide further compelling
kinetic evidence for a ligand-substituted intermediate. (53) Evidence for
covalent hydration in aquation of iron(III)-phenanthroline complexes is
mentioned in the iron(lII) section below (Section 8.2.4). The possible role
of ligand-substituted intermediates in reactions of diimine and of pyridine
ligands is also mentioned in connection with ruthenium(II) (Section 8.3.1),
platinum(IV) (Section 8.8.1), and iridium(lII) (Section 8.6). In this last
case, and in reactions of the radicals G and (SCN); with osmium(II) and
osmium(III) bipyridyl complexes, (54) the intermediacy of ligand-substituted
species is not thought likely.
Although the majority of kinetic studies deal with bidentate aromatic
diimine ligands, related ligands make appearances (e.g., 5 above). Several
aliphatic analogs are mentioned in a recent review. (55) Until last year no
mention had been made of the oxygen analog 8 of the diimine donor group
9. It now appears that mixed complexes of 8 and 9 donor ligands can exist,
and that the iron(II) complex [Fe(bipy)z(pzc)t, where pzc = the pyrazine
carboxylate anion 10, is low spin and kinetically fairly inert. (56)
8.2 Iron
(-(
I '\
N 0
8
197
9
Whereas the substitutions discussed so far concern replacement of
diimine ligands, substitution at iron (II) in the bis(diimine) 11 (R =
p-C
6
14Me) complex [FeL(MeCN)z]2+ in acetonitrile solution involves
11
replacement of the solvating MeCN molecules. The kinetic pattern for
replacement by N -methyl imidazole has been established, with rate con-
stants and activation parameters reported for replacement of the second
acetonitrile molecule, which is rate limiting. It is not possible to establish
the mechanism in acetonitrile, but in acetone solution substitution takes
place by a D mechanism. (57) This system is closely related to several in the
next section which also involve N
4
-macrocyclic ligands.
Substitution and oxidation can often both be involved in reactions of
tris(diimine)-iron(II) complexes with oxidizing agents. Thus, for example,
reaction with hydrogen peroxide involves rate-determining dissociation as
the first step. Similarly, initial dissociation seems to be the first step in the
predominant pathway for superoxide oxidation of the [Fe(phenh]2+
cation. (58) Dissociation may also be involved in reactions of diimine-iron(II)
complexes with nitrous acid. (59) Here and elsewhere it is recognized that
these complexes react with nitric acid-in the initial stages aquation may
be the only important path, but autocatalytic redox processes usually
become dominant before aquation is complete, especially for the more
easily oxidizable ligands and complexes. (60)
8.2.3. Other Low-Spin Iron(l/) Complexes
In the equilibrium and kinetic study of the reaction of iron(II)
phthalocyanine with carbon monoxide in dimethyl sulfoxide, rate laws.
rate constants, and activation enthalpies and entropies were determined. (61)
A similar study has been made of reaction of the 14-ane and 15-ane (12
and 13, respectively) complexes of iron (II) with carbon monoxide and with
rJ
c" N)
N N
V
12 13
benzyl isocyanide. Strictly we should only be considering the 14-ane com-
plex here, as this is low spin, whereas the 15-ane complex is high spin.
Indeed this difference in spin type is reflected in a two-thousand times
difference in reactivity towards carbon monoxide. For both stages in the
replacement of acetonitrile in [Fe(14-ane)(MeCNhf+ by benzyl
isocyanide a D mechanism is operative; the five-coordinate intermediates
are both nondiscriminating. (62)
For solvolysis of the water-soluble 4-N,N,N-trimethylanilinium por-
phyrin complex of iron(II), rates are proportional to the second power of
proton concentration. Rates measured for this complex, cobaJt(II) and
nickel(II) complexes of the same ligand, and for other metal(II)-porphyrin
complexes, have been correlated with Buchler's stability index. This index
incorporates charges, radii, and Pauling electronegativities. (63)
I.L -Peroxobis(phthalocyaninatoiron(II)) reacts with imidazole, in
dimethyl sulfoxide, chloroform, or toluene, to give [Fe(pc)(imh]' In the
first two solvents there is evidence for a two-step mechanism. (64)
To turn from tetradentate to bidentate ligands, bis(glyoximato) com-
plexes often undergo similar reactions to analogous complexes containing
tetradentate ligands. Thus complexes [Fe(fdHhX
2
], where fdH
2
=
a -furildioxime and X = (substituted) pyridine, 1-methylimidazole, or
butylamine, react reversibly with carbon monoxide, in a manner analogous
to systems discussed in the first paragraph of this section. A kinetic study
of such reactions, in chloroform solution, has established the operation of
a D mechanism in both directions. Rate constants and enthalpies and
entropies of activation are reported. For replacement of ligands X, 75 <
I1Ht < 106 kJ mol-I and -33 < I1St < +67 J K-
I
mol-I; for replacement
of CO (in [Fe(fdHh(CO)X]), 92 < I1Ht < 109 kJ mol-I and -2 < I1St <
+46 J K-
I
mol-I. Basicities of ligands X are important in determining
reactivities. (65)
Addition of trimethyl phosphite to acetonitrile solutions of iron(II)
salts results, eventually, in the replacement of most of the solvent molecules
8.2 Iron
199
in [Fe(MeCN)6J
2
+ by trimethyl phosphite. Replacement of the first
acetonitrile molecule is very fast. Replacement of the second molecule
takes place at rates within the stopped-flow range, and is thought to
correspond to the high-spin-Iow-spin changeover. This step is believed to
take place by an interchange mechanism, with the relative slowness (k -
1 s -1 at 297 K) attributable to steric control by the trimethyl phosphite.
Further substitution, to give [Fe(MeCNh{P(OMehh]2+ and
[Fe(MeCNh{P(OMeh}4J
2
+ is very slow.(66)
8.2.4. Iron(Ill) Complexes
The dependence of aquation rates for [Fe(SCI-phenhJ
3
+ and [Fe(SBr-
phenhJ
3
+ on solvent composition over the range 0%-100% water-sulfuric
acid has been explained on the basis of covalent hydration of the complexes
(cf. Section 8.2.2 above).(67)
Ligand exchange with dialkyldithiocarbamate complexes [Fe(R
2
dtchJ,
hinted in one source to be relatively slow, has now been confirmed(68) to
be rapid, as originally proposed a decade ago. (69) The kinetics of reaction
of [Fe (Ehdtch], and of the related morpholinediselenocarbamate (14)
f\ I
Se
-
o N-(
'---I 'Se
14
complex, with mono-, di-, and trichloroacetic acids have been monitored
in benzene solution. Activation enthalpies are about 7 kcal mol-
1
, activation
entropies large and negative, for the Ehdtc complex; a more complicated
rate law operates for the diselenocarbamate complex. (70) The kinetics and
mechanism of the relatively slow reaction of ferrioxamine B with ethylene-
diaminetetraacetate have been described.(71)
Kinetics and mechanism of water exchange at iron(III), in the form of
Fe3+ aq and of FeOH
2
+ aq, have been much studied recently. (72-74) It is now
clear that water exchange at the former takes place by an associative
mechanism, at the latter by a dissociative mechanism. Rate constants, (72-74)
activation enthalpies and entropies, (72,73) and activation volumes(74) have
been obtained from variable-temperature and variable-pressure
17
0 nmr
experiments. The activation volumes for water exchange at Fe3+(aq) and
at FeOH2+(aq) are -S.4 and +7.0 cm
3
mol-t, respectively; the former is
almost exactly the same as that reported for the isoelectronic Mn2+(aq)
ion. If acidic (HCI0
4
) aqueous solutions containing iron (III) are heated
for a time, then water exchange at the polynuclear product is over a
thousand times faster than at mononuclear Fe
3
+(aq).(73) The rate law and
rate constants have been established for reaction of Fe
3
+(aq) with
methylaquorhodoxime. The reaction is simple reversible replacement of
the intramolecular O-H'" 0 unit in [Rh(dmgHhMe(OH
2
)] by
O-Fe-O.(7S)
8.3. Ruthenium
8.3.1. Ruthenium(II)
The complexes trans-[Ru(NH
3
)4{P(ORhhf+ and trans-
[Ru(NH
3
MP(OEthHP(ORh}f+, with R = methyl, isopropyl, or butyl,
aquate to give a monophosphite product with rate constants which vary
little with the nature of the complex or solvent composition (up to 80%
ethanol). The results support the dissociative mechanism previously pro-
posed(76) for the triethyl phosphite complex. Trans effects are here domi-
nated by rr acceptor properties of these phosphite ligands. (77) Trans effects
in substitution in bis-ligand ruthenium (and iron) phthalocyanine complexes
follow the order
P(OBuh > PBu3 > pyridine - methylimidazole
Substitution is, of course, much slower in [Ru(pc)L
2
] than in [Fe(pc)L
2
].
A D mechanism operates in both series of complexes; the five-coordinate
intermediates show very little discrimination. (78) Variable-temperature
proton nmr studies of axial ligand exchange in 1-methylimidazole- and
4-t-butylpyridine-benzyl isonitrile-ruthenium-tetraphenylporphyrin com-
plexes show that tetraphenylporphyrin has a much smaller cis effect here
than in analogous iron(II) systems. Again rr-bonding effects are important
in determining kinetic parameters. (79)
The complexes [RuX2(7J-C6H6)(dmso)], X = Cl or Br, react slowly
with triphenyl phosphine in dimethyl sulfoxide, rapidly in dichloromethane,
to give [RuX
2
(7J -C
6
H
6
)(PPh
3
)]. These observations, and the rate law
established for reaction in the latter solvent [as in equation (1)] are
consistent with the limiting dissociative mechanism shown in equation (2)
(1)
[Ru] + dmso
k21 +PPh3
[Ru]-PPh
3 (2)
8.3 Ruthenium 201
with dimethyl sulfoxide an effective competitor but dichloromethane an
ineffective competitor for the transient five-coordinate intermediate
[RU].80 A transient intermediate is also involved in the reaction of the
dithioformate complex [Ru(S2CH)(PMe2Phh{P(OMeh}t with trimethyl
phosphite, catalyzed by added PMe2Ph as in equation (3). Operation of
r.d.s.
/1 st'c(
PMe
2
Ph
fast
-
h
s
/"='

I
P(OMeI
3
(3)
this mechanism is supported by the isolation and characterization of the
[Ru(S2CHPMe2Ph)(PMe2Ph){P(OMeh}t cation.(8!)
Stoichiometric and kinetic experiments have indicated the likely reac-
tion sequence and mechanisms for the reaction of trans -[Ru(NO)-
(N0
2
)4(OH)]2- with barbituric acid, which gives a violurato complex as
product. (82) Cyclic voltammetry has demonstrated the conversion of
[Ru(terpy)(bipy)(NH
3
)]2+ into [Ru(terpy)(bipy)(N0
2
W; this is oxida-
tion of the ammonia ligand, but is formally classifiable as substitution with
respect to the ruthenium(II).(83) Stopped-flow cerium(IV) oxidation, flash
photolysis, and electrochemical techniques have been used to probe the
analogous ligand modification in equation (4). Here, however, the metal
(4)
plays an important role as the proposed mechanism involves a
ruthenium(IV) intermediate. (84) The first step in the reaction of
[(H
3
N)sRuN
2
Ru(NH
3
)s]4+ with the hydroxyl radical must be adduct forma-
tion, as the rate constant is very much too fast for substitution at
ruthenium(II) and is also at least a hundred times too fast for proton
abstraction.(8S) On the other hand, proton abstraction is believed to be the
key step in deuterium exchange with [Ru(bipyh]2+ in dimethyl sulfoxide-
methanol solutions containing methoxide. Exchange occurs at the 3,3'-
positions, where the protons are slightly acidic as a consequence of steric
strain. The mechanism of this reaction is thus effectively S N 1 CB rather
than Gillardian nucleophilic attack by methoxide at the coordinated diimine
(cf. Section 8.2.2).(86) A by-product of a photochemical study of NO
z
- and
Et
3
P-substituted 2,2'-bipyridyl complexes of ruthenium(II) is the observa-
tion that [Ru(4N0
2
bipyh]2+ loses the nitro substituent quite easily by
thermal solvolysis. Interestingly the free 4N0
2
bipy ligand is inert to thermal
solvolysis, but undergoes photochemical loss of N0
2
readily.(87)
Irradiation of [Ru(NH
3
)s(acylpyridine)]2+ complexes in the metal-to-
ligand charge transfer band results in alkene generation. Quantum yields
and rates of internal conversion are reported. These processes are of
particular interest in that they represent examples of rarely encountered
upper-excited-state ligand photochemistry. (88) Photoaquation of
[Ru(bipyh]CIz in aqueous acid (HCl) gives [Ru(bipyh(OH
2
hf+ and
[Ru(bipyh(OH
2
)CIt. The pH dependence of photoaquation rates is
attributed to association between the ruthenium complex and a proton
both in the ground state and in the excited state. (89) Photolysis of
[Ru(bipyh]2+ in acetone or in acetonitrile (chloride medium) also gives
solvento species such as [Ru(bipy)z(MeCN)Clt. These reactions, like that
in water, are very slow. By way of contrast, photolysis of [Ru(bipyh]CIz
in dichloromethane fairly readily gives [Ru(bipyhCIz]. Reaction in
nitromethane or in dimethylformamide is more complicated. (90) Many other
recent references to photochemistry and photophysics of [Ru(bipyhf+ lie
outside the range of this section, being principally redox or physics; a
photochemical study(91) of bis(bipyridyl)ruthenium(II) complexes of 4-
vinyl pyridine and of poly-4-vinylpyridine casts much more light on the
chemistry of PVP than on substitution mechanisms of ruthenium(II).
Irradiation of or of its phen analog in
aqueous solution gives the A form. This is claimed to be the first example
of inversion at an octahedral center which does not involve substitutional
changes in the coordination sphere of the central metal ion. (92) For
[Ru(bipY)z(L-serine)t, irradiation converts the A into the form, whereas
for [Ru(phenh(L-serine)t the reverse, ...... A, is the case. However, it
should be added that in both these cases the equilibrium constants are
not far from unity.(93) Isomerization of cis- and of trans-
[Ru(Ph2PCH
2
CH
2
PPh2hCIz], and of the osmium analogs, is accelerated
by heat, light, or the presence of traces of ruthenium(III). In fact thermal
isomerization favors trans ...... cis, photochemical cis ...... trans. The cis isomer
is much the more labile to substitution, for instance in donor solvents such
as acetonitrile; another example of the strong trans effects of phosphorus
ligands in ruthenium(II) complexes(94) (d. start of this section).
8.3.2. Ruthenium(III)
Some qualitative ideas on mechanisms involved can be gleaned from
a detailed descriptive paper on reactions of [Ru(NH
3
)sxf+, X = CI, Br,
8.3 Ruthenium 203
or I, with thiocyanate. A range of mono-, di-, and trinuclear ruthenium(III)
products were obtained, many obtained and characterized for the first
time. (95) Relative rates of aquation and anation for cis - and trans-
[Ru(NH
3
)4Cht and [Ru(NH
3
MOH
2
)Cl]2+ have been compared and dis-
cussed.(96) Irradiation of trans-[Ru(enhht in its ligand field band results
in loss of iodide with >85% sterochemical change, but loss of iodide occurs
with complete stereoretention on irradiation in the charge transfer band.
This neat demonstration of different stereo behavior can only be carried
out for the diiodo complex, since the ligand field and charge transfer bands
overlap for trans-[Ru(enhCht and trans-[Ru(enhBr2t.(97) This study
represents a useful addition to the somewhat meager amount of information
on photochemical behavior of d
5
complexes. Stereochemical changes on
photolysis of these d
5
complexes have been discussed in relation to a
general five-coordinate-intermediate model for photochemistry of d
5
and
d
6
complexes of ruthenium, rhodium, and iridium. (98) The first example of
emission from a lowest excited ligand-to-metal charge transfer state has
been reported, for [Ru(CN)6f-. This complex was chosen as it contains
an oxidizing metal ion and a reducing ligand with a large crystal field
effect. (99)
The ruthenium(III)-7 -methylhypoxanthine complex 15 can undergo
N(3) to N(9) linkage isomerization, giving 16, in solution. At 37C the rate
3+ 3+
o Me
o Me
"t'X)
"l'X>
I I
RuINH
3
)s
RuINH
3
)s
15 16
constant is 1.25 x 10-
4
s -t, with AJl* = 90 kJ mol-
1
and as* = -31
J K-
1
mol-t, in acid solution. The rate constant is lower, 2.2 x 10-
6
s -t, in
neutral solution, as N(I) has lost its proton (Ka = 1.51 x 10-
5
).0)
Numerous modes of interconversion of various forms of ruthenium(III)-
diethylenetriaminepentaacetate in solution have been considered.oo
1
) A
large and detailed diagram is given, but unfortunately this appears to be
purely speculative, as no kinetic or other evidence is offered in support.
Reversible reaction of hydroxo-ruthenium(III) species with enolate
forms is involved in ruthenium-catalyzed oxidation of ketones by periodate.
Observed rate constants are reported, but no attempt has been made to
extricate rate constants for formation and dissociation of the
ruthenium(III)-enolate intermediatesyo2) This is excusable in the light of
the complicated overall law, but it is surprising that the authors bothered
to obtain composite IlHt and Ilst values corresponding to their observed
rate constants.
8.3.3. Ruthenium(III)/(IV)
A preliminary report of a flow resonance Raman study of aquation of
"ruthenium red," [(H3N)sRu(III)-O-Ru(IV)(NH3)4-0-Ru(III)(NH
3
ht+,
in aqueous ammonium chloride-ammonia buffers gives a rate constant of
about lOs -1 at 25C and promises details of the results of temperature
and pH variation experiments and an interpretation in the subsequent full
paper.(103) The kinetics of reaction of "ruthenium brown,"
[RU
3
02(NH
3
hS+ =: the Ru(III)Ru(IVh analog of "ruthenium red" above,
with hydroxide were reported several years ago, (104) but this and subsequent
investigations have failed to establish what happens after the initial rate-
determining hydroxide attack. The latest very brief communication points
out that oxidation of a coordinated nitrogen ligand must be involved and
suggests participation of a hydroxylamine complex. (lOS)
8.4. Osmium
8.4.1. Osmium(IIj
A series of complexes based on [OS(1/6-C6H6)]2+ provides an interest-
ing link between organometallic chemistry and the chemistry of classical
Werner complexes. The coordinated benzene takes no active part in the
latter aspect, except for its electron-withdrawing effect. [Os( 1/ 6 - C6H6)-
(en)Clr aquates with a rate constant of 1.2 x 10-
5
s -1 at 25C; the
product, [Os(1/6_C
6
H
6
)(en)(OH
2
)]2+, reacts with chloride with k
f
=
1.34 X 10-
3
dm
3
mol-
1
S-1 at 25C. The kinetic pattern for the reaction of
[OS(1/6_C6H6)(OH2hJ2+ with isonicotinamide is not simpley06)
The photochemistry of the complexes [Os(II)(terpy)LL,]"+, with L =
Ph
2
PCH
2
CH
2
PPh
2
or Ph
2
PCH=CHPPh
2
and L' = Cl-, py, MeCN, or CO,
has been examined in acetonitrile solution. All except the chloro complexes
undergo dissociative ligand loss.(107) Cis trans isomerization of
[Os(Ph
2
PCH
2
CH
2
PPh
2
hChJ has already been mentioned in Section
8.3.1. (94)
8.4.2. Osmium(lVj
Further results have appeared from Kiel on kinetics of substitution
processes in the hexahalogeno-osmate(IV) systems containing various com-
8.4 Osmium 205
binations of chloride, bromide, and iodide ligands. Kinetic data are reported
for 18 ligand exchange reactions of chi oro bromo complexes [OsClnBr6_n]2-,
n = 0-6. Rate constants and activation parameters t::.Ht and t::.st have been
obtained for all 18 reactions. Lability increases as the number of bromides
increases; these complexes are less labile than chloroiodo analogs. The trans
effect of bromide is only slightly higher than that of chloride (the difference
arises from an activation enthalpy difference of 2 kcal mol-lor less), so
ligand substitution is not stereospecific. The role of aquo intermediates is
considered.(lOB) A few further kinetic data are given in a second paper, but
this is more concerned with assessing the relative cis and trans effects of
chloride, bromide, and iodide and summarizing these and other geometrical
factors in a three-parameter equation. The best fit of the accumulated
kinetic data on these halogenoosmates(IV) yields the following relative
values for Cl: Br: 1:(109)
cis effect 1 : 1.8: 7
trans effect 1: 6 : 1000
Concentration-time profiles have now been calculated from the above
generalized expressions for specific reactions in the general
[OsClxBryl(6_x_y)]2- plus halide system. Diagrams are published for the
specific cases of cis-[OsX
4
1
2
]2-, X = Cl or Br, reacting with bromide and
chloride, respectively. In each case there are nine likely and five unlikely
intermediates en route to [OsCI
6
f- and [OsBr6]2-. Agreement between
calculated and actual results is goodYlO) This latest offering appears to
represent a summing up and consistency check on this group's extensive
kinetic activities in this area.
A paper primarily concerned with electrochemical preparations from
ttans -[ Os VI02CI4]2- gives some qualitative kinetic data on some derived
osmium(IV) complexes. Thus the half-life for the conversion of
[OsCI
4
(OH
2
h] into [{OsCI
4
(OH)}z0]2- in 1 M HCl0
4
at room tem-
perature is several days, whereas chloride anation of [OsCI4(OH2h] to
[OsCls(OH
2
)]- is complete within a day in 6 M HCl, within 2 h in
O.4M HCl + 7 M LiCI.(111)
The hexafluoroosmate(IV) anion, [OsF
6
]2-, is extremely inert to
aquation. However, aquation of this complex can be catalyzed by zir-
conium(IV); rate constants for a range of conditions have been reported.
Interestingly and surprisingly, rate constants for zirconium(IV)-catalyzed
aquation of [OsF
6
f-, [ReF
6
f-, [PtF
6
f-, and [PF
6
r are the same under
identical conditions. The rate-determining step must therefore involve only
the zirconium. Comparison of rate constants for these catalyzed aquations
with rate constants obtained in a study of de polymerization of polynuclear
zirconium(IV) species in aqueous solution shows that the catalyzed aquation
rate constants merely reflect rates of depolymerization of polynuclear
zirconium(IV) species to give catalytically more active speciesYl2)
8.5. Rhodium
Sections 8.5.1-8.5.9 deal with various facets of reactivity of
rhodium(III) complexes, arranged as far as possible in a similar order to
that adopted in Volume 1 of this series. In the last section, 8.5.10, brief
mention is made of some relatively slow reactions of dirhodium complexes
in which the metal is formally in oxidation states 2 and 21.
8.5.1. Aquation
Hydrolysis of [Rh(NH
3
h(N0
2
)]2+ and of cis-[Rh(NH
3
MN0
2
ht
results in replacement of ammonia, but hydrolysis of trans-
[Rh(NH
3
MN0
2
ht results in replacement of a nitro ligand. This pattern
parallels that established earlier for the analogous cobalt(III) complexes,
and derives from the dominance of the trans effect of NO
z
. Activation
parameters for the cobalt(III) and rhodium(III) complexes are compared.
It is concluded that ammonia loss occurs by an Id mechanism at both metals,
but that loss of nitrite has more associative character in the case of
rhodium(III). (113) Evidence from aquation, base hydrolysis, and ligand
replacement studies gives an indication of chemically nonequivalent coordi-
nation sites in [Rh(tren)ChtY
I
4)
For reaction of trans-[Rh(tnhCht, where tn = propane-1,3-diamine,
i.e., trimethylenediamine, with hydroxide in aqueous solution, kobs =
kl + k
2
[OH-]. The latter term is assigned to the expected SN1CB process.
Reactivities of analogous tn, en, and (NH
3
h complexes are compared in
a table;(l1S) there are, of course, no dramatic differences.
Acid aquation of [Rh(tren)CI
2
t gives a -[Rh(tren)(OH
2
)Clf+; base
hydrolysis gives {3 -[Rh(tren)(OH)CIt (as indeed does photolysis). Kinetics
of base hydrolysis of these three complexes are detailed. (114) Acid aquation
of [Rh(NH
3
)s(N0
2
)]2+ results in ammonia loss (see above), but base
hydrolysis results in loss of nitrite. (113)
8.5.3. Reactions in Liquid Ammonia
Rates of solvolysis of [Rh(NH
3
)sBr]2+ and of [Rh(NH
3
)s(N0
3
)]2+ have
been determined in liquid ammonia as a function of temperature and of
B.5 Rhodium 207
acidity. The conjugate base mechanism is operative; enthalpies and
entropies have been determined for the conjugate base formation equi-
librium and for the subsequent decomposition of the conjugate basesY
l6
)
The cis-[Rh(enhClzt cation reacts in liquid ammonia in two distinct steps,
corresponding to replacement of the two chloride ligands. Both steps
involve the conjugate base mechanism. Activation parameters are
for both steps; both equilibrium formation of the conjugate base and its
decomposition can be monitored for both steps. Entropies of conjugate
base formation are less negative for these rhodium complexes than for
their cobalt(III) analogs, activation entropies for reactions of the conjugate
bases are considerably lower. There is a brief discussion of the reaction of
trans -[Rh( enhI2t in liquid ammonia. (117)
8.5.4. Catalyzed Aquation
Plots of kobs against mercury(II) concentration for catalyzed aquation
of mer-[RhCh(OH
2
h] (giving cis-[RhCh(OH
2
)4t) are curved, permitting
evaluation of the equilibrium constant for formation of the intermediate
adduct and of the rate constant for dissociation of HgCI+.o18) The equi-
librium constant for adduct formation is 758 dm
3
mol-
1
(at 19C), sur-
prisingly larger than the value of 137 reported earlier
(119
) for the fac isomer.
The various equilibrium and kinetic parameters for the mer isomer are
tabulated below (Table 8.1).0
18
) The AS* and A V* values are consistent
with a dissociative mechanism with no charge creation; the A V
t
value of
+8.1 cm
3
mol-
1
here
(118
) may be compared with AV* = + 14.3 and
+21.5 cm
3
mol-
1
for mercury(II)-catalyzed aquation of [RhCI
s
(OH
2
)]2-
and [RhCI
6
f-, respectively. (120) The small value of A V-G- for adduct forma-
tion presumably represents the balance between an intrinsic negative
volume change and a positive contribution from partial desolvation of the
Hg2+ on incorporation into the adduct. HgCI+ is nearly as effective as a
Table B.l. Equilibrium and Kinetic Parameters for Adduct
Formation and Dissociation in the mer-[RhCMOH
2
)3] Plus
Hg2+ Reaction, in Aqueous Solution at 23C
(from Ref lIB)
Equilibrium adduct formation
K = 788 dm
3
mol-I
AHG- = +6.3 kJ mol-I
AS-G-= +76 J K-
1
mol-I
A V-G- = +2.8 cm
3
mol-I
Adduct dissociation
k = 1.11 X 10-
3
s-I
AH" = +90 kJ mol-I
AS" = +4 J K -I mol-I
A V" = +8.1 cm
3
mol-I
208 8. Substitution Reactions-Nos. 6 and Above: Other Inert Centers
catalyst as Hg2+ in these systems, but HgClz exhibits negligible catalytic
effect. (118) a v-G- for adduct formation between [Rh(NH
3
)sI]2+ and Hg2+ is
again small (-1.7cm
3
mol-
1
); av* for dissociation of HgI+ is
+ 1.2 cm
3
mol-i. This a v* value is felt to reflect considerable interaction
with incoming water in the transition state-in other words associative
interchange. (121)
In mercury(II)-catalyzed aquation of cis-[Rh(enhClzt, formation of
the binuclear intermediate is rapid and essentially complete when the
mercury(II) is in excess. Rates of dissociation of the intermediate decrease
slightly on going from water to 20% or 40% methanol. This smallness of
effect can be attributed to relatively light solvation of the leaving HgCI+
group, and should be contrasted with the larger effects of solvent variation
when Cl- is the leaving group from inorganic or, even more markedly,
organic centers. An analysis of the observed solvent trend for cis-
[Rh(enhCI(ClHg)]4+ dissociation into initial state and transition state con-
tributions is only possible by the devious expedient of using transfer
parameters for the transition state in the trans-[Co(enhClzt /Hg
2
+ reaction
for initial state transfer parameters here. (122)
8.5.5. Formation
Kinetics of reaction of [Rh(NH
3
)s(OH
2
)]3+ with propionate in aqueous
solution are consistent with the usual two-step Eigen-Wilkins mechanism,
involving propionate or propionic acid according to the pH. Comparisons
with other rhodium(III) and analogous cobalt(III) reactions suggests that
the interchange step in the reaction under discussion has considerable
associative character. (123) Similar conclusions apply to the reactions of
trans-[Rh(NH
3
)4(OHht and, probably, [Rh(NH
3
)s(OH)f+ with ammonia.
Here the pH dependence of rate constants indicates that OH
2
rather than
OH- is the leaving groupY24) The two steps in the reaction of [Rh(tren)-
(OH
2
h]3+ with chloride are kinetically distinguishable; the intermediate is
(3 -[Rh(tren)(OH
2
)Clf+ Y 14)
8.5.6. Solvent Exchange
Solvent exchange at the [M(PR
3
h(solvhH
2
t cations, with M = Rh or
Ir, R = phenyl or cyclohexyl, solv = acetone or acetonitrile, have been
followed by proton nmr spectroscopy, with the establishment of rate con-
stants and Arrhenius parameters. The most marked feature is the enormous
acceleration induced by the trans effect of the hydride ligand, taking these
reactions from the normal very slow rates characteristic of rhodium(III)
and iridium(III) into the nmr time scale. Rates are considerably faster for
8.5 Rhodium 209
the rhodium complexes than for the iridium complexes, owing to smaller
ARt values for the former. The acetone solvates are much more labile
than the acetonitrile solvates, again attributable to lower t::..Ht values. The
markedly positive t::..st values observed in all cases are attributed to the
operation of a dissociative mechanism; this is consistent with the trans
effect of the hydride mentioned above. (125)
8.5.7. Ligand Replacement
Observed first-order rate constants for reaction of trans-[Rh(tnhCht,
tn = 1,3-propanediamine, with bromide are independent of bromide con-
centration, as indeed they are for all similar systems except one. The
rate-determining step is replacement of the first chloride by water, with
subsequent bromide anation and replacement of the second chloride
quicker. (115) Qualitative kinetic observations, including solvent effects, have
been described for replacement of dialkyl sulfides by pyridine or bipyridyl
in [Rh(SRzhCh]. (1Z6)
8.5.8. Ring Opening and Closing
Rate constants have been determined for the forward and reverse
reactions shown in equation (5) in which LL = (0 -dimethylaminophenyl)-
dimethylarsine bonded through nitrogen and arsenic, L = this ligand bon-
ded only through arsenic, and X = SCN-, SeCN-, NO
z
, N
3
, or pyridine.
trans-[Rh(LLhcht + X mer-[Rh(LL)LChX]"+ (5)
k,
The rate constant involving ring opening, kz, is little affected by the nature
of X, but k1 is much affected thereby. A dissociative mechanism is believed
. h . 1 d' . (127)
to operate 10 t e nng c osure, mer to trans, uectlOn.
8.5.9. Photochemistry
Possible excited state reaction schemes are suggested to account for
emission lifetimes and their apparent activation energies, effects of added
anions (OH-, CN-, on emission, and final products in photoaquation
of [Rh(NH3)5Cl]2+ (Cl- only lost) and [Rh(NH
3
)sBr]z+ (both Br and NH3
lost)Y28) Photoaquation rates for bromide loss are much greater for cis-
and trans-[Rh(NH3)4Br2t than for [Rh(NH
3
)sBrf+. Ammonia loss is also
much faster from the cis-dibromo complex than from [Rh(NH3)sBrf+.
Combination of new measurements on emission lifetimes with published
data on quantum yields permits the estimation of reaction rate constants
for the ligand field excited states, and thus a more detailed understanding
of the cis- and trans-labilizing effects of ammonia and of bromide in these
three complexes. (129) Ligand field excited state lifetimes have been com-
pared for [Rh(NH
3
)5Br]2+, [Rh(NH
3
)sCI]2+, and [Rh(NH
3
)6]3+ in the sol-
ution and solid states. (130)
There have been several reviews of mechanisms of photosubstitution
in rhodium(III) complexes. Bond indexes for ground and excited states
have been discussed in relation to D2h species.(13l) The observation of
stereospecificity has been discussed in relation to lifetimes for triplet
singlet deactivation and geometric rearrangements. (98) Direct evidence has
been presented to support the intermediacy of, and role of rearrangement
in, five-coordinate intermediates in ligand field irradiation experiments. (132)
Rhodium(III) has been discussed in relation to cobalt(III) and
iridium(III)/133) and to ruthenium(II) and ruthenium(III) as well.(98)
8.5.10. Oxidation States 2+, 2.5+
Rates of reaction of [Rh
2
(OAc)4t with bromide and with chloride are
intermediate between rates of substitution at rhodium(II) in [Rh
2
(OAc)4]
and at rhodium(III). There must therefore be some fairly strongly bonded
water ligands in the [Rh
2
(OAc)4t cation, which is believed to have one
water coordinated to each rhodium. (134) The techniques used in a
calorimetric and spectrophotometric examination of [Rh
2
(butyrate)4] indi-
cate that compound to be substitution labile. (135)
8.6. Iridium
The characterization(136) of [Ir(en)CI
4
f and of mer-[Ir(en)(enH)CI
3
]
should assist mechanistic studies in this area. Solvent exchange at
hydridoiridium(III) cations is dealt with in connection with rhodium(III)
analogs in Section 8.5.6, q.v.
The nature of the [Ir(bipyh(OH
2
)]3+ cation continues to be probed.
Neither recent paper favors covalent hydration. An X-ray study was inter-
preted in terms of the structure shown as 17, on which two comments must
17
8.8 Platinum(IVj 211
be made. Firstly, in the proposed O .. H-N unit the hydrogen was not
located, its presence was only inferred from the 0 to N distance. Secondly,
it not poggible to distinguish bdween C and N atoms In the bipyridyls.
However, infrared and nmr evidence favors the structure shown in 17. (137)
13C-nmr spectra of this iridium(III) species in water and in dimethyl
sulfoxide are very different. No evidence was found for an Sp3 carbon. The
structure proposed here, 18,(138) includes the monodentate bipy ligand so
18
often suggested in this cation. As usual, neither of these groups has studied
or discussed phenanthroline analogs. Structure 17 is surely impossible for
a tris(l, lO-phenanthroline) complex, and structure 18 would involve much
steric interference.
Two papers give information relating to solvent effects in photo-
chemistry of iridium(III)-diimine complexes;(139.140) mechanisms of photo-
b
. 'd' (III) f . . . I (98 133)
su stltutlon at In mm eature In two reVIew artlc es. .
B.7. Nickel(lII)
There is a brief discussion of kinetics of complex formation of
nickel(III) complexes of tetraazamacrocyclic ligands such as cyclam with
chloride, bromide, thiocyanate, and sulfate in a review of the synthesis and
reactions of nickel(III) complexes. (141) Such reactions are really rather
fast-it is at d
6
nickel(IV) that slow substitution may be expected, if not
obscured by rapid oxidation of ligands.
B.B. Platinum(IV)
B.B.l. General
There is some discussion of interconversion mechanisms in complexes
of the type [Pt(IV)(amino acid)L
2
Xyr+, where L2 = en or (NH
3
h and X
and Yare taken variously from CC Br-, OH-, and OH
2
, in an article on
ring formation and alkaline hydrolysis. (142)
The first example of pseudo base formation with coordinated pyridine,
as opposed to 2,2' -bipyridyl or l,lO-phenanthroline and their derivatives,
has been suggested for the reaction(143) in equation (6). This claim has been
[ yrJl ptIPY)'(I-], H'
2+
[ Ptlpyl4 CIa] + H aO
(6)
disputed(144) and defended;(145) an alternative explanation involving seven-
coordinate platinum(IV) would be equally fascinating!(143)
The concept of electron catalysis permits new correlations in organic
and in inorganic mechanisms. The application to inorganic chemistry is
illustrated with reference to substitution at platinum(IV). (146)
8.8.2. Inversion at Coordinated Sulfur and Selenium
It is very rare to find a six-membered chelate ring which is purely
inorganic, but such is the case with the [Pt(S5h]2- anion. It is difficult to
decide what process involving these inorganic rings (19) is responsible for
19
the observed line coalescence in variable-temperature 195Pt nmr (CD
3
0D
solution), but the barriers are 45.1 and 50.5 kJ mol-
1
for the two directions.
These are on the low side in comparison with inversion barriers in the MS
5
rings in (11
5
-C
5
H
5
hM(S5) (M = Ti, Zr, or Hf)Y47)
The program of investigations of inversion barriers at sulfur and
selenium coordinated to platinum(IV) in progress at Exeter, discussed in
Volume 1 of this series, has produced two further publications. Energy
barriers, quoted in terms of k, E
a
, 10gA, ao*, ill*, and as*, have been
evaluated for intramolecular processes in CDCh and C
6
D
5
N0
2
solutions
of [PtXMe3(MeSRSeMe)], with R = CH
2
CH
2
(X = CI or I) or o-C
6
H4
(X = CI or Br). The low-temperature barriers (CDCh solutions) are due
to inversion at sulfur and/or selenium; assignment is complicated by the
fact that there are four chemically distinct ground states and four transition
states. The barriers observed at higher temperatures in C
6
D
5
N0
2
are due
to intramolecular scrambling which seems to involve all the methyl groups.
8.8 Platinum(IV) 213
A whole-molecule contortion involving a pseudo-eight-coordinate
platinum(IV) transition state is suggestedY48) Novel fluxional rearrange-
ments have been probed by nmr for new binuclear complexes of the type
Me Me
Me 1/
I X-Pt-Me
Me-Pt/ X/ I
/1 /S
Me S -CHR I
\CHR CHR
'E/
20
shown in 20. Here E = CH
2
or S (trithian ring), R = H or Me, and X = CI,
Br, or I. The following types of rearrangement may occur(149):
(i) R = H, E = S. The trithian ring is in the boat form; a barrier
!lot = 58.6 kJ mol-
1
applies to a process
involving 60 pivoting of the cyclic ligand with
respect to the platinum-sulfur bonds, which
averages CH
2
and CH
3
environments. At
higher temperatures scrambling by ligand dis-
sociation and recombination is possible.
(ii) R = H, E = CH
2
Pivoting is not now feasible, but the higher-
temperature scrambling process can still
operate.
(iii) R = Me, E = S. The trithian ring is now in the chair form, and
the methyl ligands prevent pivoting at rates fast
enough to cause nmr line coalescence.
This type of investigation has recently been extended to chromium and
tungsten carbonyl derivatives of sulfur and selenium ligands of this class. (150)
Chapter 9
Substitution
Reactions of Labile
Metal Complexes
9.1. General
Lincoln and coworkers(1) have drawn attention to an important analytical
problem which might be encountered when the temperature-dependent
nmr technique is used to study exchange reactions obeying a two-term rate
law reflecting competition between a first- and a second-order process. In
general, of course, the Arrhenius plot for such a system will be curved but
the activation parameters and the limitations to the concentration range
over which measurement is possible may conspire to produce an accidental
linearity, which in turn could lead to a mechanistic oversimplification for
the system. Such misinterpretation of exchange data can, it is suggested,
be reduced through the use of a statistically weighted nonlinear least-
squares method which minimizes the residuals between the experimental
data and those generated by the appropriate two-term transition-state
equation [equation (1)], where TA is the site lifetime and [B] the concentra-
tion of the exchanging species.
TAl = (kT/h){exp(-!::.Hi/RT + !::.Si/R)
+[B] exp(-Mfi/RT + (1)
215
216 9 Substitution Reactions of Labile Metal Complexes
9.2. Complex Formation Involving Unsubstituted Metal
Ions: Unidentate Ligands and Solvent Exchange
9.2.1. Bivalent Ions
The likelihood of a gradual changeover in mechanism from fa to fd
for solvent exchange at the bivalent metal cations Mn2+, Fe
2
+, C0
2
+, Ni
2
+,
given such support recently by the elegant high-pressure nmr studies of
Merbach and others, has been referred to by Tanaka(2) in a note updating
an idea suggested in 1976. Expressing the activation enthalpy of the
solvent-exchange process in the form in equation (2) (where I1Hd and I1Hv
(2)
are, respectively, the enthalpies of solvent dissociation from the metal ion
and evaporation of the solvent), he has reevaluated the coefficients a and
b which are characteristic of the metal ion and reflect the dissociative
character of the reaction. Through a least-squares treatment of the exchange
data involving acetonitrile, ammonia, N,N -dimethylformamide, dimethyl-
sulfoxide, methanol, and water, he has derived the following values of a
and b, respectively: Mn
2
+ = 0.448, 0.592; Fe
2
+ = 0.605, 0.802; C0
2
+ =
0.791,0.867; Ni
2
+ = 0.917,0.978. A central assumption in this analysis
is that for these four ions (and six solvents) the mechanism is independent
of the solvent. This question, which was also discussed in Volume 1, page
194, has been considered again by Swaddle and coworkers(3l in a paper
reporting the solvent exchange parameters for acetonitrile on
manganese(II) and iron(II), as determined by 14N nmr line broadening.
They note that although the ratio of the volume gain (or loss) on releasing
(or coordinating) a molecule of solvent on passing to the transition state
for solvent exchange by dissociative (or associative) activation (i.e., 11 V
t
/
where is the molar volume of the solvent) actually varies significantly
from solvent to solvent for a given metal ion (presumably reflecting the
"openness" of the solvent), the value of 11 V
t
is fortuitously rather similar
for a given metal and the general trend can indeed be taken to indicate
the gradual changeover from predominantly associative (Mn
2
+) to pre-
dominantly dissociative (Ni
2
+) activation, as already noted. Although the
entropies of activation exhibit the same trend as 11 V
t
(as is to be expected),
it is pointed out that there are particular uncertainties associated with the
estimation of I1st by nmr line-broadening and these should engender a
distinct reluctance to draw detailed mechanistic conclusions from the values
obtained.
In contrast, no such invariability of mechanism apparently holds for
ligand exchange at beryllium(lI). Lincoln and Tkaczuk(4-6l have used the
variable-temperature proton nmr technique to investigate the exchange of
9.2 Complex Formation Involving Unsubstituted Metal Ions 217
a range of oxygen ligands (L) on [BeL
4
r+ in various noncoordinating
solvents. They analyzed the data in terms of the rate law (3) with the results
exchange rate = 4(k
l
+ (3)
shown in Table 9.1. (While assigning the k2 term to an A mechanism, they
point out that an interchange mechanism cannot altogether be ruled out
on the evidence currently available; if the latter were operative, however,
they are confident that it would be associatively activated.) Lincoln and
Tkaczuk point out that for this series of ligands the Gutmann donor number
increases with the size; thus, since both trends would be expected to lead
to an increased tendency to exchange through a D mechanism, it is not
possible to apportion the relative mechanistic importance of these ligand
characteristics on the basis of these data alone. They also discuss the role
of the non coordinating solvent in determining the relative importance of
A and D mechanisms (cf. the discussion on exchange at Sc(III) noted in
Volume 1, page 196) and feel that it is connected with its molecular charac-
teristics rather than its bulk properties. Strehlow et al. (7) have used the
pressure-jump technique to study the formation of BeS04 in mixtures of
water and hexamethylphosphoric triamide (HMPT). The formation rate
clearly depends on the composition of the solvate species
[Be(HMPT)x(H
2
0)4_x]2+ and on whether an HMPT or H
2
0 molecule is
being replaced, but the relaxation is complicated and a full analysis is not
attempted.
Several ligand-exchange studies have been made on six- and four-
coordinate unidentate ligand complexes of magnesium(II) and zinc(II) but
so far it has not proved possible to determine the rate law and parameters
for the same ligand on both metal ions. (Since Mg2+ and Zn
2
+ have similar
ionic radii, any mechanistic differences for the exchange reaction should
reflect the difference in "hardness" between the two metals.) A further
attempt, using the ligand triphenylphosphine oxide in CD
2
Clz solution,
was also unsuccessful(S) as the predominant exchanging species appeared
to be [Zn(O=PPh
3
)4r+ and, interestingly, [Mg(O=PPh
3
)s]2+ (although a
small amount of [Mg(O=PPh
3
)4r+ was also thought to be present). In
both cases a D mechanism is postulated with, for ZnL4' k
ex
(200 K) =
611 37 s-t, MI!x = 32.0 0.7 kJ mol-t, dS!x = -28.3 3.4 J K-
1
mol-I, and for MgL5' k
ex
(220 K) = 38 4 s-t, MI!x = 73.7 1.8 kJ
mol-t, dS!x = 123 8 J K-
I
mol-
l
(per L molecule in both cases). This is
the first report of ligand exchange at five-coordinate magnesium.
A further high-pressure nmr investigation of acetonitrile exchange at
cobalt(II) in pure acetonitrile has been reported, (9) yielding the parameters
k(298 K) = (2.56 0.06) x 10
5
s-t, MI* = 48.8 1.1 kJ mol-t, dS* =
+22.2 3.7 J K-
I
mol-t, d V* = +7.7 1.7 cm
3
mol-I.
T
a
b
l
e

9
.
1
.

K
i
n
e
t
i
c

P
a
r
a
m
e
t
e
r
s

f
o
r

L
i
g
a
n
d

E
x
c
h
a
n
g
e

o
n

.
.
.
.
.

0
0

A
s
s
i
g
n
e
d

k
1
(

3
4
0

K
)

k
2

(
3
4
0

K
)
/

S
o
l
v
e
n
t

m
e
c
h
a
n
i
s
m

d
m
3

A
H
t
/
k
]

A
S
t
/
]

R
e
f
.

O
=
C
M
e
(
N
M
e
2
)

a

D

7
.
3

5
6
.
9

-
6
2
.
1

6

O
=
C
M
e
(
N
M
e
2
)

a

A

1
0
.
5

6
6
.
7

-
3
0
.
1

6

O
=
C
M
e
(
N
H
M
e
)

a

D

9
.
2

7
1
.
5

-
1
7
.
3

6

O
=
C
M
e
(
N
H
M
e
)

a

A

1
6
.
3

7
6
.
8

+
3
.
1

6

O
=
C
H
(
N
M
e
2
)

a

D

7
.
4

8
3
.
6

+
1
6
.
3

6

O
=
C
H
(
N
M
e
2
)

a

A

1
7
6

5
8
.
1

-
3
2
.
0

6

\
Q

O
=
C
(
N
M
e
2
h

a

D

7
2
.
6

7
7
.
1

+
1
6
.
4

4

O
=
S
M
e
2

a

A

2
0
5
0

5
1
.
1

-
3
2
.
3

4

O
=
P
M
e
(
O
M
e
)
(
P
h
)

a

A

8
.
5

6
8
.
7

-
2
6
.
1

5

V
:
l

O
=
P
M
e
(
O
M
e
h

e

A

1
9
.
1

6
0
.
2

-
4
4
.
4

1
1
4

:
:
:
:

<
:
:
l
-
O
=
P
(
O
M
e
h

e

A

2
6
.
6

5
6
.
0

-
5
4
.
0

1
1
4

;
:
;
.

O
=
C
M
e
(
N
M
e
2
)

b

D

1
8
.
1

7
8
.
0

+
7
.
5

6

O
=
C
M
e
(
N
M
e
2
)

b

A

1
0
.
5

6
7
.
8

-
2
6
.
9

6

;
:
:
s

O
=
C
M
e
(
N
H
M
e
)

b

D

3
8
.
3

7
4
.
7

+
4
.
0

6

O
=
C
M
e
(
N
H
M
e
)

b

A

1
9
.
3

8
2
.
9

+
2
2
.
6

6

'
"

s
:
:
,

O
=
C
H
(
N
M
e
2
)

b

D

4
1
.
6

6
3
.
0

-
2
9
.
8

6

'
"
'

O
=
C
H
(
N
M
e
2
)

b

A

1
8
3

6
0
.
2

-
2
5
.
6

6

;
:
:
s

'
"

O
=
C
(
N
M
e
2
h

b

D

1
4
7

7
9
.
8

+
3
0
.
2

6

.
.
s
;
,

O
=
P
M
e
(
O
M
e
)
(
P
h
)

b

D

2
0
.
9

6
2
.
6

-
3
6
.
6

5

t
"
-
<

O
=
P
M
e
(
O
M
e
h

b

D

2
6
.
3

6
4
.
3

-
2
9
.
7

5

s
:
:
,

<
:
:
l
-
O
=
P
M
e
(
O
M
e
h

b

A

1
1
.
9

6
9
.
4

-
2
1
.
3

5

O
=
C
H
(
N
M
e
2
)

c

D

2
2
.
0

4
0
.
8

-
1
0
0

6

O
=
C
H
(
N
M
e
2
)

c

A

1
0
5

4
4
.
0

-
7
7
.
8

6

O
=
P
M
e
(
O
M
e
)
(
P
h
)

c

D

4
4
.
3

5
9
.
8

-
3
8
.
6

5

9

O
=
P
M
e
(
O
M
e
h

c

D

8
1
.
3

7
7
.
8

+
1
9
.
4

5

;
:

O
=
P
(
O
M
e
h

d

D

6
5
.
3

5
6
.
9

-
4
3
.
9

1
1
5

'<
:
:
s

>
<

a

C
D
3
N
0
2
.

h

C
D
,
C
N
.

c

C
D
2
C
1
2
.

d

C
H
2
C
l
2
.

e

C
H
,
N
0
2

'
"

'
"

The single relaxation observed in the ultrasonic absorption of
copper(II) formate, acetate, and propionate has been used(1O) to evaluate
a rate constant (20C) for water substitution by carboxylate at Cu
2
+ of
(3.4 1.2) x 10
8
S-I. The enthalpy of activation is 10 1 kcal mol-
1
for
the formate, and it was confirmed that the ligand derived from the strongest
acid forms the weakest copper complex.
Zinc chloride and (under some conditions) zinc nitrate solutions in
aqueous DMSO, on the other hand, yield(11) two ultrasonic absorption
maxima: with the chloride this is taken as evidence for an octahedral-
tetrahedral coordination change accompanying the addition of the third
bound Cl-, while with the nitrate the high-frequency relaxation (observable
only at low-water-mole fractions) is attributed to outer-sphere complex
formation. The rate constants (25C) for solvent loss with the nitrate
(X
H20
= 0.59) and the chloride (X
H20
= 0.039 and 0.904) are, respec-
tively, 2.2 x 10
8
,4.1 X 10
7
, and 3.3 x 10
7
S-I.
A single relaxation is found(12) for cadmium nitrate in methanol,
dimethylformamide, and dimethylsulfoxide in the temperature range 15-
45C and the concentration range 0.02-0.25 mol dm -3, which yields solvent
exchange rate constants of, respectively, 1.1 x 10
8
, 6.5 X 10
7
, and 5.3 x
10
7
S-I. The values reported for t:J/* are 9.6, 22.6, and 14.2 kJ mol-
1
and
the large negative activation entropies (-60, -19, -49 J K-
1
mol-I) suggest
that an fa mechanism is operating.
9.2.2. Ions of Valency 3 and Higher
Further evidence has been found(13) for the importance of steric effects
on the rate of ligand exchange at [ScL
6
]3+ in a non coordinating solvent
(CD
3
CN). Assuming the two-term rate law (4), Pisaniello and Lincoln
exchange rate = 6k
ex
(k
1
+ (4)
obtained rate constants (300 K) of 87, 13.3, 12.5 (s-\ k
1
) and 419, 167,
18.1 (dm
3
mol-
1
s-\ k
2
), respectively, for L = N-methylacetamide, N,N-
dimethylacetamide, and N,N- diethylacetamide. Although the activation
parameters do not show definite trends from which mechanistic conclusions
may be drawn, it is considered significant that when the solvent is changed
to CD
3
N0
2
the parameters for the dimethyl ligand do not change
significantly, while those for the diethylligand do. This type of behavior
has already been noted in other Sc(III) systems, as well as in Be (II) and
dioxouranium(VI) systems, and indicates that interactions outside the first
coordination sphere are significant. A linear free energy relationship is
shown to exist for ligand substitution on scandium(III) and the mechanistic
implications of this are touched upon.
Two recent
17
0 nmr studies(14,IS) on solvent water exchange on
iron(III) seem to provide definitive evidence for the notion that the substitu-
tion pathway involving the hexaquo ion is associatively activated while that
involving the hydroxy form is dissociatively activated. Temperature varia-
tion at atmospheric pressure has yielded(14) the following kinetic param-
eters for exchange on, respectively, [Fe(OH
2
)6]3+ and [Fe(OH
2
)s(OH)f+:
k(s -\ 25C) = (1.6 0,2) x 10
2
, (1.2 0,1) x lOs; mol-I) =
15.3 0.6, 10,14 0.35; (cal K-
I
mol-I) = 2.9 1.6, 1.26 0.95,
while the volumes of activation for the two ions are reported
OS
) to be -5.4
and +7.0 cm
3
mol-I. (Another temperature-variation study on water
exchange at iron (III) has been published(16) which involved solutions in
1.5 m HCI0
4
.) Variable-pressure measurements with iron(III) in DMSO,
DMF, and methanol provide(17) an interesting comparison with these
results: in methanol, even in highly acidic solutions, the cation present is
[Fe(MeOH)s(OMe)]2+ and the volume of activation (+6.4 0.2 cm
3
mol-I)
for solvent exchange is consistent with an fd mechanism, while in the other
two solvents the exchanging species is the hexasolvate and the values of
v* (-3.1 0.3 and -0.9 0.2 cm
3
mol-\ respectively) provide evidence
for an fa mechanism. Meyer et al. list(17) the known values of V* for
solvent exchange on the ions Sc
3
+, Cr3+, Fe
3
+, and Ga
3
+ (Table 9.2) and
note that they provide evidence for a similar gradual change in mechanism
fron'!. associative to dissociative activation as that already found in the
divalent ions Mn2+, Fe
2
+, C0
2
+, and Ni
2
+. In. both cases the changeover
occurs after the d
S
ion (i.e., after Fe
3
+ and Mn
2
+) and the authors speculate
as to why this should be.
Mentasti et al. have reported(IS) a very interesting study of the kinetics
of complex formation between iron(III) and the highly-charged non basic
ligands [Fe(CN)6]3-, [CO(CN)6]3-, and [Mo(CN)s]4- (in water). They also
measured the stability constants of the 1: 1 complexes (which, not surpris-
Table 9.2. Volumes of Activation (em
3
mol-I) for Solvent
Exchange on Hexasolvated Metal Ions (Ref 17)
Sc Cr Fe Ga
dO
d
3
d
5
, h,s,
d
lo
H
2
O - 9.3 -5.4
DMF -6.3 -0.9 + 7.9
DMSO -11
- 3,1
+13.1
(CH
3
OhPO - 20.7 +20.7
Suggested A,fa fa fa fd
mechanism
ingly, they found to be highly sensitive to ionic strength) and were able to
evaluate directly both Kos (the outer-sphere equilibrium constant for the
labile aquo ion) and K
is
(the ratio of the species associated in the inner
and outer spheres of the Fe
3
+ ion). The rate constants (25C) for the entry
of the three anions into the inner sphere of the cation (i.e., for the
outer-inner sphere interchange) are, respectively, 42, 51, and 410 S-I. This
type of variation is, of course, typical for an Ia mechanism but there will
be some, no doubt, who feel that the authors are being a little overenthusias-
tic in suggesting from these results that complex formation at all tervalent
aquocations might involve such a mechanism. Dash and Harris(19.20) have
studied the formation of the iron(III) complexes of [(NH
3
)sCOC
2
0
4
t and
(salicylato )pentaminecobalt(III) [where the pentamine residues are 5NH
3
,
(enh(NH
3
), and tetraethylenepentamine] and have observed parallel path-
ways involving [Fe(OH
2
)6]3+ and [Fe(OH
2
)s(OH)]2+ to which they assign,
respectively, fa and fd mechanisms. The well-studied formation of iron(III)
thiocyanate has been used(21) to test a technique for the simultaneous
determination of kinetic and thermodynamic parameters by fast-reaction
methods.
(5)
The ligand exchange of OPMe(OMe)Ph( = L) on yttrium(III) in CD
2
Ch
solution obeys(22J the rate law (5) with k
1
(215 K) = 312 13 s-t, Mli =
31.4 1.4 kJ mol-t, asi = -48.4 6.6 J K-
1
mol-t, and k
2
(215 K) =
455 31 dm
3
mol-
1
S-I, = 35.2 2.8 kJ mol-t, = -27.6
12.7 J K-
1
mol-t. As with previously obtained equations of this type, the
kt term is assigned to a D mechanism and the k2 term to an A mechanism.
With L = O=C(NMe2h only the kl term is observed(23) (with CD
3
CN as
solvent), the derived kinetic parameters being k
1
(250 K) = 25 1 s-t,
Mli = 27.1 0.5 kJ mol-t, and asi = -108 2 J K-
t
mol-I. Com-
parison of these results with those for related ligands where the exchange
was too rapid for quantitative investigation suggests(22) that the coordination
number and the lability of the yttrium(III) species increases as the size of
the ligand decreases. The exchange parameters for DMF on [Tm(DMF)sf+
are(24) k(200 K) = 2.94( 0.09) X 10
4
s-t, MI* = 33.2 0.5 kJ mol-t,
as* = 9.9 2.4 J K-
1
mol-t. It is not considered(24) appropriate to use the
small positive as* as diagnostic of the mechanism.
The exchange of N,N- diethylacetamide (AcNEt2) in [U0
2
(AcNEhh]2+
in CD
2
Ch and CD
3
CN solution obeys a first-order rate law and yields(25) the
parameters k
t
(265 K) = 54.8 8.3, 38.0 5.2 s-t; Mli = 68.3 1.2,
76.5 1.1 kJ mol-I; and asi = 47.1 4.6, 75.0 4.0 J K-
1
mol-t, respec-
tively; these are consistent with the operation of a D mechanism in each
case. Comparison of these with previous data on ligand exchange at
dioxouranium(VI) demonstrates that the changeover from aD to a possible A
mechanism for this species (see Volume 1, page 196) is not linked in any
simple way with either the size of the ligand or its electron-donating ability (as
indicated by the Gutmann donor number).
9.3. Complex Formation Involving Unsubstituted
Metal Ions: Multidentate Ligands
9.3.1. Univalent Ions
Rate constants for the formation and dissociation of several alkali
metal ion cryptates have been reported(26-28): these are given in Table 9.3,
where k
f
is the formation rate constant and kd and kHA are, respectively,
the direct and acid-catalyzed dissociation rate constants. (Cf. Volume 1,
page 198, Structure 1, with m = 0, n = 1 for (2,1,1), m = 1, n = 0 for
(2,2,1), and m = n = 1 for (2,2,2); a subscript B indicates that a benzene
ring has been added between the two oxygens in one of the bridges, and
a subscript D that an alkyl chain (-ClOH21) has been substituted on one
of the two carbons between a pair of bridging oxygens.) The overall effect
Table 9.3. Rate Constants for Formation and Dissociation of Alkali Metal
Cryptates at 25C
kr/ kHA/
Cryptate Solvent
dm
3
mol-
1
s-
1
k
d
/s-
1
dm
3
mol-
1
S-1
Ref.
[Na(2
B
, 2
B
, 2)t a

5.0 x 10
2
26
[K(2,2,2)t a
4.5 x lOB
0.003 1.5 x 10 27
[Na(2,2,2)t a 3.3 x 10
4
27
[Na(2
B
,2,2lt a 6.7x 10
3
26
[K(2
B
,2,2lt a 5.8 x 10
7
0.0057 1.7 x 10 26
[K(2
B
,2
B
,2lt a 2.9 x 10
7
0.0203 1.4 26
[Rb(2,2,2lt a
1.8 x lOB
0.17 2.4 x 10 27
[Rb(2
B
,2,2lt a
1.3 x lOB
3.32 1.3 x 10
2
26
[Rb(2
B
,2
B
,2lt a 8.0 x 10
7
18.8 26
[Na(2
B
,2
B
,2)t b 4.9x10
7
1.2 28
[Na(2
o
,2,2lt b 4.2 x 10
7
3.7 28
[K(2
B
,2
B
,2lt b
1.5 x lOB
0.27 28
[K(2
0
,2,2)t b
1.2 x lOB
0.047 28
[Rb(2
B
,2
B
,2lt b
1.1 X lOB
130 28
[Rb(2
o
,2,2)t b 7.4x10
7
0.54 28
a Propylene carbonate.
b Methanol.
9.3

Unsubstituted Metal Ions: Multidentate Ligands 223
Table 9.4. Rates of Dissociation (s -I) of Cryptates in Various Solvents at 25C
(Ref. 29)
Crypt ate Ethanol DMSO DMF N -Methylpropionamide
[Li(2, 1, 1)t
6.0 x 10-
4
2.12 X 10-
2
1.40 X 10-
2
4.8 X 10-
3
[Na(2, 1, lW
7.1 X 10-
1
ca. 5
4.7 x 10-
1
[Ca(2, 1, 1)]2+ ca.2 x 10-
1
[Li(2, 2, IJt
ca. 1.3 x 10
[Na(2, 2, IJt
2.62 x 10-
3
7.5 X 10-
1
2.5 X 10-
1
1.67 X 10-
1
[K(2, 2, 1)t
1.35 x 10-
1
ca. 2.6 1.35
[Rb(2, 2, 1)t 1.1 x 10
[Cs(2, 2, IJt ca. 2 x 10
3
[Ca(2, 2, 1)]2+ 8.0 X 10-
4
[Na(2, 2, 2Jt
3.0 x 10-
1
5.68
[K(2, 2, 2Jt
4.08 x 10-
3
2.68
4.0 x 10-
1
1.33 X 10-
1
[Rb(2, 2, 2Jt
9.17 x 10-
2
5.0 X 10-
1
[Ca(2, 2, 2)f+
4.4 X 10-
2
of the substituents is to increase kd and reduce k
f
. The dissociation rates
kd are also found(29) to be very sensitive to solvent (Table 9.4), covering a
range of more than nine orders of magnitude. (Except for the (2,1,1)
cryptates, the values of k
f
, calculated from kd and the equilibrium constants,
are all within the range 10
6
_10
9
dm
3
mol-I S-I.) kd increases sharply with
increasing donor number of the solvent, but the results for water are out
of line with the rest being much higher (and the formation rates rather
lower) than expected. This, it is suggested, might be associated with hydro-
gen bonding between water and the 0 and N atoms of the ligands.
The kinetic deuterium solvent isotope effects on the acid-catalyzed
dissociation of Li(2,1,lt and Ag(2,2,2t have been reported,(30) as have
the exchange kinetics(31) of cryptand (2,2,1) on T1(2,2,2t and Tl(2
B
,2,2t.
The kinetics of complex formation between Li+ and 18-crown-6 ether in
1,3-dioxalane and 1,2-dimethoxyethane solvents have also been
reported. (32)
9.3.2. Bivalent Ions
The ultrasonic technique has been used(33) to study the binding of
calcium to sorbitol: the interaction is weak and the formation rate constant
(40C) could only be approximately determined as (1-2) x
10
8
dm
3
mol-
1
S-I. The kinetics have also been studied of the dissociation
of calcium cryptates in various solvents(29,30) (see Table 9.4) and of cryp-
tand exchange(31) at Ca
2
+ and Pb
2
+. The formation of Ca(2, 1, 1)2+ has been
followed(34) by means of the recently developed thermal stopped-flow
technique, and low-temperature stopped flow has been used(35) on the
formation and dissociation of Sr(dibenzo-18-crown-6)2+ in methanol.
The formation rate constant for the nickel(II)-inosine complex
(790 dm
3
mol-
I
S-I; 15C) is(36) similar to that for the adenosine complex
and comparison of the stability constant with that of the adenosine complex
suggests that a five-membered chelate ring is involved. Both values of kr
are, however, some 3-5 times lower than those of neutral monodentate
ligands like imidazole and ammonia and it is suggested that a steric effect
of the ribose moiety might be responsible for this reduction. The data for
reaction of Ni
2
+ with inosine 5' -monophosphate (IMp2-) are interpreted(36)
in terms of a stepwise process: the rate of the first step (k
l
= 1.6 X 10
4
s -I;
15C) is fairly typical for substitution at [Ni(H
2
0)6f+, while that of the
second step (k2 = 3.9 X 10
3
S-I; 15C) is substantially lower, presumably
also because of steric effects. Evidence has been obtained(3?) for a similar
steric control in the reaction of Ni2+ with vanillomandelic acid, mandelic
acid and thiolactic acid (k
r
= 3.6 x 10
3
, 4.9 X 10
3
, and 7.7 x
10
3
dm
3
mol-
I
s -I, respectively; 25C) although in these cases the possibility
of rate-limiting deprotonation from the internally-hydrogen-bonded ligand
could not be ruled out. The effect of ring size on chelate formation between
nickel(I1) and aminomethylpyridine analogs has also been discussed, (38)
while the nickel-malonate reaction has been studied again(39) by pressure
jump. The formation of L-glutamate complexes of Ni2+ exhibit(4o) "normal"
kinetics.
The effect of acid on the rate of chelate-ring opening at nickel(II) has
been studied further(41-43) by Margerum and coworkers. It had generally
been assumed that the only way in which acid could assist in the dissociation
of a polyamine complex of Ni2+ (or any other metal ion) was by protonation
of a donor atom after it had been replaced in the inner coordination sphere
by a water molecule. However, it is also conceivable that protonation could
occur before or during the solvation of the metal ion and there had been
indications that such an alternative mechanism was important at low pH.
Further data have now been published(4!) on the acid-catalyzed ring opening
in Nj2+ -ethylenediamine( en) complexes which bear on this problem. The
dissociation rates of [Ni(en)]2+ and [Ni(enhf+ have a pH-independent
term and they also increase linearly with [H+] at pH values below 1.5; in
addition, general-acid catalysis occurs in the former case (but not the latter)
in the presence of mono-, di-, and trichloroacetic acids. This the authors
see as evidence for the acceleration of chelate dissociation by protonation
of one of its N atoms without the intervention of a solvent molecule and
they suggest that the unusual variation in the rate constants for these
carboxylic acids (which decrease as the acid strength increases) reflects
9.3 Unsubstituted Metal Ions: Multidentate Ligands 225
their ability to associate with the metal complex and to transfer a proton
to the N atom as it leaves the inner sphere. (A similar mechanism involving
parallel water substitution and protonation of the bound ligand has been
suggested(44) for the dissociation of the nickel(II) complex of ethy-
lenedibiguanidine.) General-acid catalysis is well established for the dissoci-
ation of nickel(II) triglycine but it has now been shown(42) that mixed-ligand
complexes, in which the second and third ligands block axial coordination
by the solvent, are not general-acid catalyzed. The case of nickel(II)
glycylglycyl-L-histidine is(43) the most complicated reported to date, the
major mechanistic pathway(s) depending on pH and the concentration of
general acid present.
There have been further reports on the rate enhancement observed
when the "normal" complex [Ni(pada)f+ is formed in the presence of
micelles. These can be very considerable but it has been found(4S) that
sodium alkanesulfonates are about 25% less effective in this respect than
the alkyl sulfates. (46) The effect of various anionic polyelectrolytes on this
reaction has also been studied:(47) it ranges from an acceleration of about
two orders of magnitude in the case of poly(styrene sulfonate) to a retarda-
tion by about one order of magnitude for polyphosphate and seems to be
dependent on the state of hydration of the Ni2+ ion when "condensed" in
the polyelectrolyte domains. Polyphosphate exerts(48) a similar retardation
on the formation of [Co(pada)f+ and the effect is attributed to the complete
replacement of the coordinating water by the polyelectrolyte. Activation
volumes for the formation of the pada complexes of Ni
2
+ and C0
2
+ in
water, DMF, and DMSO have been reported:(49) all the values are rather
close and variation in the anion (CIO;, BPh;, appears to produce
no systematic change.
The effects of adding varying amounts of DMSO to water on the
kinetics of formation of [Ni(bipy)f+ have been studied(SO) by the stopped-
flow technique. All the evidence suggests that at DMSO mole fractions
(X2) less than -0.2 very little DMSO gets into the inner coordination
sphere of the cation, so the effect of changing the solvent structure on the
rates can be investigated without the complication of any changes in the
nature of the reacting species. The values of ill} and as} both decrease
sharply between X
2
::::: 0.1 and 0.2(aHj = 50.9 1.0,41.5 0.8 kJ mol-I;
as} = -15 3, -45 3 J K-
I
mol-I, respectively), having changed little
in the range 0 :s; X
2
0.1, and it is suggested that in this case the changes
in solvent structure have a greater effect on the initial state than on the
transition state. The effect of the addition of urea on the kinetics of nickel(II)
malonate formation in aqueous solution has also been investigated:(Sll at
urea concentrations below 3 mol dm -3 the variation in kr can be rationalized
simply in terms of the effect on the solvent dielectric constant, but above
this concentration it is thought that urea enters the inner coordination
sphere of the metal ion.
The rate constants for the formation of 1 : 1 complexes of some dialkyl-
2,2' -bipyridyl-5,5' -dicarboxylates with Ni
2
+ in methanol have been corre-
lated(52) with the Taft modification of the Hammett equation; this result
is consistent with there being an inductive effect from the alkyl groups.
Comparison of the rate constants and activation parameters for the reac-
tion of Ni2+ with 2,6,9,13-tetraazatetradecane, 1,4,B,1l-tetraazacyclo-
tetradecane, and N,N',N",N"'-tetramethyl-1,4,B,11-tetraazacyclo-
tetradecane in DMSO and DMF indicates(53) that the same mechanism
holds in the first two cases (dissociation of the first solvent molecule in the
outer-sphere complex) but that steric effects are dominant with the third
ligand.
The mechanism of 1 : 1 complex formation between palladium(II) and
catechol and 4-methylcatechol has been studied(54,55) in acidic media, and
the rate of 1: 1 (and 1: 2) complex formation between silver(II) and several
diols is(56) an order of magnitude higher in basic solution than in acidic.
The kinetics of formation and dissociation of the complex between cop-
per (II) and cryptand (2,2,1) in aqueous DMSO have been measured(57)
and the dissociation rate constant, in particular, found to be strongly
dependent upon water concentration. The kinetics of the formation of the
zinc(II) and mercury(II) complexes of 2-methyl-2-(2-pyridyl)thiazolidine
have been measured,(58) as they have for the metal exchange reaction(59)
between Cu
2
+ and the nitrilotriacetate complexes of cobalt(II) and lead(II).
Two pathways are observed(60) for ligand transfer between Ni(II), Cu(II),
Zn(II), Cd(II), Pb(II) and Hg(II) and their dithiocarbamate complexes in
DMSO: the first involves dissociation of the ligand from the complex
followed by substitution at the metal ion, while the second involves direct
electrophilic attack by the metal ion on the dithiocarbamate complex. As
expected, the relative importance of the pathways depends on the stability
of the complex and the lability and electrophilic character of the metal ion.
9.3.3. Ions of Valency 3 and Higher
The kinetics of aluminum(III) complex formation with chromotropic
acid and 3-hydroxypicolinic acid have been studied(61) by the stopped-flow
method. In the former case the reaction is thought to involve primarily
AIOH
2
+ and the undissociated ligand (k
f
= 3.B x 10
2
dm
3
mol-
1
S-l; 25C),
while for the latter there is evidence for the participation of AhOH
2
+ as
well as the more commonly observed routes involving A1
3
+ and AIOH
2
+.
The aqueous aluminum(III) propionate system has been investigated by
the pressure-jump technique:(62) two relaxations, attributed, respectively,
9.4 The Effects of Bound Ligands 227
to the formation of the mono and bis complex, were observed. Two further
stopped-flow studies have been reported on the formation of complexes
of vanadium(III) in water; they involved the malonate(63) and 5-nitrosalicy-
late(64) dianions.
Both the Fe
3
+ and the FeOH
2
+ pathways appear to be(65) important
in the reaction of iron(III) with 5-chloro-, 5-nitro-, 6-hydroxy-, and 3,5-
dinitrosalicylic acid but, it is suggested, only the latter features in the
reactions with mandelic acid, (66) tiron, (67) 2,7 -dichlorochromotropic acid, (67)
and citric and tartaric acids. (68) Mechanistic analyses have also been given
of the reaction of iron(III) with pyridoxamine and pyridoxal,<69) and with
thiocyanate in DMSO-water mixtures. (70)
9.4. The Effects of Bound Ligands
9.4.1. Reactions in Water
The dissociation of the first ligand molecule from [CrL
3
f+ (with
L = bipy,(71) phen,(71) 4,4'-dimethylbipy,(72) and 5,5'-dimethylbipy(72) fol-
lows a first-order rate law; the kinetic parameters (25C, pH 5.3) are,
respectively, kd = 0.390, 0.0643,1.17,0.663 S-I; = 84.4, 89.0, 81.5,
89.9 kJ mol-I; = 30.6, 30.3, 30.1, 53.5 J K-
I
mol-I.
The rate constant (k = 7.41 x 10
4
S -t, 25C) and activation parameters
(MIt = 15.6 kcal mol-I; = 16.1 cal K-
I
mol-I) have been measured(73)
for the ligand-exchange reaction in the tris(L-proline) complex of
manganese(II), which has also been shown to contain octahedrally coordin-
ated Mn2+ with each ligand binding at the ring nitrogen and one of the
carboxylate oxygens.
The reversible binding of NO to aquairon(II) and to the citrate,
bis(acetylacetonate), and edta complexes of Fe(II) exhibits(74) second-
order/first-order kinetics, with a wide spread of rate constants (25C):
kr = 7.1 x 10
5
, 4.4 X 10
5
, 4.0 X 10
2
, ;?;6.0 X 10
7
dm
3
mol-I S-I; kd =
1.5 X 10
3
,6.6 X 10
2
,24, ;?;60 s-t, respectively. At ligand concentrations of
less than 1 mol dm -3, the replacement of H
2
0 in pentacyanoaquaferrate(II)
by 2-methylpyrazine exhibits(75) clean second-order kinetics (k" 25C =
475 dm
3
mol-I s-t, MI; = 16.0 kcal mol-t, = 7.7 cal K-
I
mol-I)
which are pH-independent in the range 6.6::; pH::; 11.4 and consistent
with the operation of a dissociative mechanism. The reactions of
[Fe(CN)50H2]3- with cysteine, penicillamine, glutathione, and 2-mercap-
toethylamine, on the other hand, exhibit a marked pH dependence and
Macartney and McAuley(76) have been able to derive rate constants for
the species H4L +(kd, H
3
L(k
2
), H2L -(k
3
) and, in the third case, He- (k
4
),
as shown in Table 9.5. The marked dependence of k on the charge of the
Table 9.5. Second-Order Rate Constants (dm
3
mol-
I
S-I) for the
Formation of [Fe(CN)sLj"- at 25C, 1= 0.50 mol dm -3 (Ref 76)
Ligand
kl k2 k3 k4
Cysteine 900 330 70
Glutathione 950 370 220 35
Penicillamine 850 350 70
Mercaptoethylamine 850 200 30
entering ligand but its insensitivity to the nature of the binding atom (N
or S) are consistent with the operation of a dissociative mechanism here also.
The kinetics of the reversible ternary complex formation between
[Ni(trien)f+ and phen or glycine have been studied(77) as a function of pH.
In both cases the reaction is first order in [Ni(trien)f+, but whereas with
phen it is first order also in the incoming ligand, in the latter case it is first
order only at low glycine concentration and tends towards a zero-order
dependence at higher concentrations. This behavior is consistent with the
formation of a singly bonded (trien)Ni-O-N(glycine) intermediate in rapid
equilibrium with reactants (with equilibrium constant 6.9 x 10
2
mol-
1
dm
3
,
25C) coupled with a rate-limiting ring closure (k = 1.3 x 10
2
S-I) in the
latter case. In the case of 1,1 O-phenanthroline the value of kr is 7.9 X
10
3
dm
3
mol-
1
s-t, which is some 34 times less than that expected on the
basis of the known water-exchange rate constant and assuming rate-limiting
water loss: presumably, therefore, ring closure is important here also.
Ternary complex formation between imidazole and [Ni(nitrilotriacetate)r
has also been studied(78) and the
17
0 nmr technique has been used(79) to
determine the square-planar-octahedral equilibrium kinetics in the
1,4,7,10-tetraazacyclododecanenickel(II) system.
The relatively rigid geometry of [Cu(tren)(OH
2
)]2+, precluding the
operation of the dynamic J ahn-Teller effect, has been generally held
responsible for the comparatively low rates of water exchange and ternary
complex formation in this species. Cayley et at. have now measured(8o) the
rate parameters for the formation and dissociation of a series of pyridine
ternaries (Table 9.6) and have found them to depend strongly on the nature
of the ligand. The fact that both formation and dissociation values largely
parallel the pKa values of the ligands suggests an associative mechanism
for substitution, and this conclusion is supported by the fact that the
activation energy for water exchange in [Cu(tren)(OH
2
)]2+ is 43.4
1.25 kJ mol-I: if substitution were dissociatively activated the activation
energy would be equal to (or greater than) this value, but in all cases it is
less than it. The comparatively large, negative values of ilS* (Table 9.6)
T
a
b
l
e

9
.
6
.

K
i
n
e
t
i
c

P
a
r
a
m
e
t
e
r
s

f
o
r

t
h
e

F
o
r
m
a
t
i
o
n

a
n
d

D
i
s
s
o
c
i
a
t
i
o
n

o
f

[
C
u
(
t
r
e
n
)
F
+
-
P
y
r
i
d
i
n
e

C
o
m
p
l
e
x
e
s

a
t

2
5
C

(
R
e
f
.

!
J
O
)

L
i
g
a
n
d

p
K
a

1
O
-
5
k
f
/
d
m
3

m
o
l
-
1

S
-
1

t
l
.
H
i
/
k
J

m
o
l
-
1

t
l
.
s
j
/
J

K
-
1

m
o
l
-
1

1
O
-
3
k
d
/
s
-
1

m
o
l
-
1

K
-
1

m
o
l
-
1

3
-
C
h
l
o
r
o
p
y
r
i
d
i
n
e

2
.
8
5

0
.
3
5

3
5
.
7
1

-
3
8
.
0
0

3
.
4
6

2
8
.
2
5

-
8
2
.
2
7

P
y
r
i
d
i
n
e

5
.
6
4

1
.
6
7

2
5
.
0
6

-
6
0
.
7
6

1
.
3
3

4
2
.
0
1

-
4
4
.
0
4

3
-
M
e
t
h
y
l
p
y
r
i
d
i
n
e

6
.
1
4

2
.
0
8

1
7
.
9
0

-
8
2
.
9
6

0
.
9
2

4
6
.
0
0

-
3
0
.
3
6

4
-
M
e
t
h
y
l
p
y
r
i
d
i
n
e

6
.
4
8

2
.
4
8

1
8
.
3
7

-
7
9
.
9
1

0
.
8
2

4
1
.
6
3

-
4
9
.
3
3

-
I
:
:
.
.

'
"

'
"

'
"
'

O
:
:
l

<
:
>

s
:
:

;
:
,
:

$
:
>
.
.
.

t
-
<

;
:
,
:

t
;
-

230
9 Sublititution Reactions of Labile Metal Campi.:;,;,;.;
and their dependence on the nature of the ligand again favor an associative
mechanism. The authors draw attention to previous conclusions that the
substitution reactions of distorted octahedral copper(II) complexes occur
by a dissociative mechanism (through substitution of the relatively weakly
bound axial water followed by Jahn-Teller inversion which places the
substituted ligand in an equatorial position) and speculate that the elemen-
tary steps in the catalytic cycle of the enzyme monoamine oxidase might,
on the contrary, involve associatively activated substitution at the copper
sites, the rate of copper-bound water exchange in this enzyme being close
to that found for [Cu(tren)(OH
2
)]2+.
Nuclear magnetic resonance relaxation studies on ligand exchange
have been reported for a series of CUL2 complexes (L = glycine, (81) a - and
f3 -alanine, (82) en, (82,83) pn, (82) bipy, (84) glycylglycine, (85) serine, (83)
threonine, (83) and aspartic acid(83) and for bis(iminodiacetato )zinc(II). (86)
The anation of [Pd(1,1,7,7-Et4dien)(OH2)]2+ and [Pd(1,1,4-
Et
3
dien)(OH
2
)f+ by Cl- have been studied(87) in a high-pressure stopped-
flow apparatus. The kinetic parameters are seen as evidence for an associa-
tively activated mechanism; they are, respectively, k = 4.2 0.1, 1558
68 dm
3
mol-
l
s-t, 25C; Mit = 13.4 0.4, 10.5 0.7 kcal mol-I; ASt =
-10.71.2, -8.72.3caIK-
1
mol-
l
; and AV
t
=-3.00.2, -2.7
0.2 cm
3
mol-I.
The kinetics have been reported for the formation(88) of several edta-5-
sulfosalicylate ternary complexes of lanthanide ions, and ligand substitu-
tion(89) in trimalonatovanadium(III) with edta
4
- and nta
3
-. Reports have
also appeared on the formation(69) of ternary complexes involving Fe(III),
pyridoxamine, and pyridoxal and the formation(90) of bis- and tris(acetohy-
droxamato)Fe(III); and activation volume evidence has been provided(91)
for a dissociative mechanism in the reaction of thiocyanate with
diaqua[meso -tetrakis(N -methyl-4-pyridyl)porphinato] cobalt(III).
The kinetics of fluoride ion exchange in the oxovanadium(IV) glycine
and fluoride mixed complexes [VO(gly)glyFr and of oxalate exchange in
[VO(oxhf- have been studied(92) by 19F and l3C nmr methods, and the
formation of the complexes by stopped-flow measurements. In all cases
the reactions were first order in both entering ligand and the
oxovanadium(IV) complex, and the overall rate appeared to depend
significantly on the charges involved.
The high-pressure stopped-flow technique has been used(93) to study
the formation of the peroxo complex of (nitrilotriacetato )dioxovanadate(V).
The rate law is as in equation (6) where kl = 7.05 dm
3
mol-
l
S-l and
d[VO(02)(nta)2-]/dt = (k
1
+ k
2
[H+])[V0
2
(nta)2-][H
2
0
2
] (6)
k2 = 1.46 X 10
4
dm
6
mol-
2
s -2 (25C, 1 atm, I = 1.05 mol dm -3), and the
activation volumes are, respectively, -3.4 0.5 and + 1.5 0.5 cm
3
mOrl.
An associative mechanism is favored. Ligand substitution kinetics of edta 4-
or edda
2
- by nta
3
- in vanadium(V) complexes have also been reported.(94)
9.4.2. Reactions in Nonaqueous Solvents
The observed rate constant for the reaction between phthalocyaninato-
iron(1l) and an excess of CO in DMSO has(95) the form in equation (7)
kobs = kf[CO] + kd (7)
with k
f
= 1.28 X 10
3
dm
3
mol-
1
S-1 and kd = 0.12 S-1 at 20C. The values
of MI* and as* are, respectively, 14, 17.5kcalmol-
1
and +3,
-3 cal K-
1
mol-t, and the authors favor a dissociative mechanism notwith-
standing the low activation entropies. The influence of the basicity of the
axial ligands on the reaction of CO with a series of bis(a -furil-
dioximato)iron(II) complexes in CC4 solution has been investigated.(96) It
has been confirmed(97) in a study of CO and O
2
binding to iron-copper
cofacial diporphyrins and strapped hemes in benzene that distal steric
hindrance can affect ligand binding to hemes, but it seems that the effect
is largely limited to a reduction in kf, kd being essentially unaffected. An
interchange mechanism is proposed(98) for the formation of
[Fe(NCMe)4{P(OMehhf+ from [Fe(NCMe)6f+ and trimethyl phosphite
in acetonitrile. In a very interesting nmr study on solvent exchange at
Co(ll), Dickert and Hellmann(99) have found that in mixtures of methanol
and DMF, the rate for the strong donor (DMF) is decreased and that for
the weak donor (MeOH) is increased, relative to the situation in the
pure solvent, as the other component is added (Table 9.7). In addition,
Table 9.7. Kinetic Parameters for Exchange of Coordinated DMF and Methanol
at Co(ll) Ions (Ref. 99)
[Co(*MeOH)6f+
[Co(DMF)(*MeOHhf+ eq
[Co(DMF)(*MeOHhf+ ax
[Co(DMFh(*MeOH)4f+
[Co(DMF)4(*MeOHhf+
[Co(*DMF)(MeOHhf+
[Co(*DMFh(MeOH)4f+
[Co(*DMFh(MeOHh]2+
[Co(*DMF)4(MeOHhf+
[Co(*DMF)6f+
k(243 K) k (298 K)
/8-
1
/8-
1
M{t/kJmol-
1
.1S
t
/JK-
1
mol-
1
25
265
1320
2100
2450
1.7 X 10
4
6.0 X 10
4
1.1 X 10
5
2.2 X 10
5
9.7 X 10
5
3.4 X 10
3
2.1 X 10
4
3.0 X 10
5
3.6 X 10
5
56.3
53.3
55.9
55.4
47.9
24.1
24.9
38.4
41.4
47.9
a trans-Iabilizing effect is apparent for the axial methanol in
[Co(DMF)(MeOHhf+, and similar trends are observed in a limited study
with methanol and another strong donor, hexamethylphosphoric acid
triamide. The behavior is rationalized(99) in terms of Gutmann's donor-
acceptor approach to molecular interactions. The presence of 15-crown-5
(acting as a quadridentate ligand) in the inner coordination sphere of
cobalt(II) reduces(100) the exchange rate of the remaining solvent molecules
(methanol and/or DMF). Further work has been reported(1Ol) on ligand
substitution reactions of tetrahedral cobalt(II) complexes solubilized in
reverse micelles, and the kinetics and mechanism of the reaction of
cobalt(II) protoporphyrin IX dimethyl ester with pyridine and related
ligands in predominantly alcoholic media in the presence and absence of
air have been discussed. (102)
Convincing kinetic evidence has been presented(103) for the existence
of a solvent path [similar to that well known in platinum(II) chemistry] in
ligand substitution at four-coordinate trans-N
2
0
2
chelate complexes of
nickel(II). Thus, for the substitution of a bidentate ligand HB (acetyl-
acetone, benzoylacetone, dibenzoylmethane, trifluoroacetylacetone, 8-
hydroxyquinoline, or N -ethylsalicylaldimine) into bis(N-R-salicyl-
aldiminato)nickel(II) complexes (with R = Et, i-Pr, or t-Bu) in methanol,
2-propanol, or toluene, a two-term rate law [equation (8)] is observed. In
rate = (k
s
+ kHB[HB])[complex] (8)
methanol (and with R = t- Bu) the rate constant k .. describing the solvent
path, and the corresponding activation parameters /1ll* and !l.S* do not
depend on the nature of the entering ligand but kHB does so strongly. The
relative contributions of the two pathways to the overall rate seem to be
governed by the conformational equilibrium planar tetrahedral of the
original complex, the planar isomer favoring the ligand-dependent path
kHB and the tetrahedral form the solvent path k
s
The factors influencing
the ligand path (especially the donor ability, acid strength, and
stereochemical properties of the entering ligand and the Lewis acidity of
the substrate) are discussed and the present results are compared with
those from corresponding systems involving copper(II).
A similar two-term rate law has been found, and the kinetic parameters
determined, for ligand substitution in four bis(N -alkylsalicy-
Iideneiminato)copper(II) complexes: (a)(104) with HB = N -ethyl- or N-
phenylsalicylideneimine and alkyl = ethyl, isopropyl, or t-butyl in alcoholic
medium; and (b)(105) with HB = N -ethylsalicylideneimine and alkyl =
t- butyl in various aprotic organic solvents. Mass-action retardation has also
been observed. (106)
Rate constants and activation parameters for the axial ligation of
zinc(II) meso -tetraphenylporphyrin by pyridine, 2-methylpyridine, and imi-
dazole in aprotic solvents are close to, but significantly different from, the
diffusion-controlled values, and it appears(107) that desolvation (either of
the base or the metalloporphyrin) is an important step in these reactions.
The mechanism of axial ligand substitution with a series of
ruthenium(II) phthalocyanine adducts is(108) dissociative (D), the five-
coordinate intermediate possessing little or no ability to discriminate
between nucleophiles. The cis effect of tetraphenylporphyrin is(109) con-
siderably less in Ru(III) complexes than in their Fe(II) analogs. An estimate
of the relative labilizing effects of the ligands L-L and Cl- in the com-
plexes [Pd(L-L)Ch] (where L-L = 1,2-bis(diphenylphosphino)ethane,
o -phenylenebis(dimethylarsine), en, phen, bipy, or 1,2-bis(phenylthio)-
ethane) have been made(llO) through a study of the reaction of these
complexes with en.
A preliminary report(l1l) has appeared which demonstrates that the
chloride ion has a substantial trans-Iabilizing effect in (tetraphenylpor-
phinato )chromium(III) chloride, and the first kinetic study on substitution
at five-coordinate manganese(III) [involving the reaction of chlorobis(/3-
diketonato)Mn(III) complexes with other /3 -diketones] has been pub-
lished. (112)
The kinetics of the hydrolysis of arsenate(V) triesters have been
studied(113) by the stopped-flow technique. It was only possible to obtain
data on the first step [equation (9)] although it could be demonstrated that
OAs(ORh + H
2
0 OAs(OH)(OR)z + ROH (9)
the second and third steps were also fast. For trimethylarsenate in methanol
solution the reaction was first order in both ester and water, with
kl = 73 dm
3
mol-
1
S-1 (25C), Mit = 13 kJ mol-r, and LlSt =
-167 J mol-
1
K-
1
The hydrolysis rates decreased in the order methyl>
ethyl> n -pentyl > i -propyl and an associative mechanism is proposed.
Part 3
Reactions of
Organometallic
Compounds
Chapter 10
Substitution and Insertion
Reactions of
Organometallic
Compounds
10.1. Substitution Reactions
10.1.1. Introduction
A short review of Basolo(1,2) emphasizes that an associative mechanism for
ligand replacement in 18-electron organometallic complexes may be found
when the reaction intermediate can avoid a 20-electron configuration by
having a ligand present that functions as an electron sink. Most commonly
this ligand is a 7T-hydrocarbon (e.g., 7j 6 _ arene -+ 7j 4 -arene or 7j 5 -
C5H5 -+ 7j 3 - C
5
H
5
) or nitrosyl (linear -+ bent). A review on transition metal
clusters(3) contains sections concerning cluster formation, breakdown, and
ligand substitution reactions.
Several particularly important papers have shown that electron transfer
chain catalysis, a mechanism known to hold for some substitution reactions
in organic chemistry and some racemization and/or substitution reactions
in classical inorganic chemistry, can provide a facile pathway for ligand
substitution in organometallic complexes. Rieger(4) reported the first
organometallic example of ligand substitution initiated and catalyzed by
electron addition. Wrighton (5) showed that electron transfer to photo excited
237
238 10 Substitution and Insertion Reactions
organometallics can lead to substitution via a chain mechanism. Kochi(6.7)
found that electron transfer from metal carbonyls can initiate a catalytic
substitution reaction. These investigations are discussed in Sections 10.1.3
and 10.1.4.
The dimeric complexes [M
2
(COho] (M = Mn or Re) continue to be
actively studied. The presence of 17-electron free radicals, [M(CO)s], as
intermediates in the thermal substitution reactions, and the chemistry of
these and other 17 -electron complexes are the questions being addressed.
Substitution reactions of cobalt and iridium carbonyl clusters, with an
attempt to define and separate electronic and steric effects, has also been
an especially active area. This chemistry is discussed in Section 10.1.4.
10.1.2. Carbon Monoxide Replacement in Mononuclear Metal
Complexes
Transition metal carbonyl hydrides of the first transition series undergo
unusually rapid substitution reactions, e.g., [HMn(CO)s] is much more
reactive than [ClMn(CO)s]. Carbonyl hydrides of most heavier transition
metals are not unusually labile. Pearson(8) proposes the hydride migration
mechanism shown in Scheme 1 to account for the unusual lability. For this
Scheme 1
H L
M-CHO
I I I
C C C
o 0 0
L L
--+
-co I
H
mechanism a relatively weak M - H bond is required, in agreement with
the known weaker M - H bond strengths for first and some second transition
series metals. Rapid CO loss from the intermediate formyl complex is due
to the expected cis-labilizing effect of a formyl group. A weak M-H bond
may be expected to lead to easy thermal decomposition with H2 evolution,
and in fact most of the metal carbonyl hydrides that rapidly substitute a
CO also are thermally unstable.
[CpV(NO)zCO] + PR
3
---+ [CpV(NO)zPR
3
J + CO (1)
Reaction (1) is reported(9) to follow a dissociative (D) mechanism for
a variety of phosphines and phosphites at room temperature in THF. In
view of the known tendency of metal nitrosyls to replace CO with PR
3
via
10.1 Substitution Reactions 239
an associative (A) mechanism, the observation of a D mechanism for
reaction (1) is surprising. Insufficient information is presented(9) to justify
the mechanistic assignment, and this reviewer feds the r@:lch@d
may be incorrect. [CpV(COhHr was found(10) to catalyze CO substitution
by PPh
3
in [CpV(CO)4] to yield [CpV(COhPPh
3
]. This interesting reaction
is suggested to follow a chain mechanism with the rate-determining step
being electron transfer to give [CpV(CO)4L which rapidly dissociates CO,
reacts with PPh
3
, and is reoxidized.
The acetate ligand in [M(CO)sOzCMer (M = Cr, Mo, or W) is strongly
cis labilizing, comparable to chloride. (11.1Z) A detailed study(1Z) of 13
CO
exchange with M = W shows that an equatorial CO dissociates stereoselec-
tively to give cis-[W(CO)4(13CO)(OzCMe)r. Labilization of CO exchange
also occurs in many metal carbonyls in the presence of BU3POY3) Equation
(2)
(2) gives a typical example. The reaction presumably proceeds by replace-
ment of NH3 by BU3PO, which exerts a cis-labilizing effect on coordinated
CO. The authors conclude that the CO-labilizing ability of BU3PO is a
transition state effect similar to that discussed by Brown(14) some years ago.
Thermal scrambling of 13CO in [M(COM
13
CO)L] (M = Mo or W;
L = phosphine or phosphite) can occur by intermolecular or intramolecular
pathways. A simple method to distinguish between these is based on
13C_13C spin-spin coupling between axial and equatorial CO ligandsY
S
)
Thus heating cis-[Mo(CO)4e
3
CO)PMe
z
Ph] at 75C in heptane for 12 h
produces substantial amounts of [Mo(COh(
13
COhPMe
z
Ph] having both
an axial and equatorial
13
CO as shown by the presence of 13C_13C coupling.
This indicates an intermolecular mechanism for CO rearrangement. With
cis-[W(CO)4(
13
CO)P(OMeh] the CO rearrangement gives product with
only one 13CO, consistent with an intramolecular mechanism. 13C labeling
experiments show(16) that the reaction of [(phen)M(CO)4] (M = Mo or W)
with MeCN to give fac-[(MeCN)(phen)M(COh] occurs via dissociation
of an axial CO and that the remaining CO ligands scramble statistically
during the conversion. The same result was found earlier with
[(phen )Cr( CO )4].
Information about the stability and stereoselectivity of coordinately
unsaturated metal carbene complexes is important for understanding a
number of reactions, including olefin metathesis and cyclopropanation. A
study of 13CO exchange in [(CO)sMC(OMe)(Ph)] (M = Cr, Mo, or W)
shows(17) that the carbene ligand is cis labilizing compared to CO. Rate-
determining CO loss is inferred from the similar rates of 13CO exchange
and cis-CO substitution by phosphines. Measurements of the ratio cis-
13CO / trans- BCO as a function of percent BCO incorporation imply that
the intermediate formed by loss of a cis-CO is captured by 13CO before
arrangement can occur when the metal is Mo. The fluxional behavior could
not be determined with Cr and W. It is concluded that the coordinatively
unsaturated carbene [(CO)4MC(OMe)(Ph)J is a kinetically viable inter-
mediate in many types of reactions of metal carbenes. The reaction of the
carbene complex [(CO)sCrC(OMe)(Ph)] with arylalkynes in dibutyl ether
gives naphthol complexes according to equation (3).0
8
) A mixture of
) + co
Cr(CO)3
(3)
isomers having R I and R
2
interchanged are produced. A kinetic study
suggests the simple dissociative mechanism shown in Scheme 2 in which
Scheme 2
k,
[(CO)sCr(OMe)(Ph)] [(CO)4CrC(OMe)(Ph)] + CO
L,
products
the alkyne competes with CO for the vacant site in the coordinatively
unsaturated intermediate. For kb !!:J{* = 108 2 kJ mol-I; AS* =
26 6 J K-
I
mol-I.
The carbyne complexes [(CO)sCrCNEt
2
t and trans-[(X)(CO)4-
CrCNEt
2
J (X = CI- or r) react with PPh
3
in 1,2-dichloroethane by a CO
dissociative mechanism to give trans-[(PPh
3
)(CO)4CrCNEt
2
t and mer-
[(X)(PPh
3
)(COhCrCNEt
2
J with PPh
3
and the carbyne ligand cis in the
latter complexY9)
Cathodic reduction of Group VI carbonyls [M(CO)6J and [M(CO)sPR
3
J
in the presence of PR
3
or THF leads to facile substitution of CO and/or
PR
3
(20) This method may be a useful alternative to the usual photochemical
synthesis, and most likely proceeds by rapid dissociation of a CO or PR
3
ligand from the reduced (19-electron) complex. Laser pulse photolysis of
[W(CO)6J in methylcyclohexane at room temperature produces
[W(CO)5S], where S is a weakly bound solvent molecule.(21) This intermedi-
ate reacts rapidly with 4-acetylpyridine (L) to give [W(CO)sL] according
to Scheme 3. At 20C, k1 = 1.9 X 10
6
s-
1
and k
2
/L
1
::::: 270. Photolysis of
Scheme 3
[W(CO)6] h., [W(CO)sS] + co
k
[W(CO)sS] [W(CO)s] + S
L,
[W(COh] + L [W(COhL]
[CpMo(COhMe] in frozen gas matrices at 12 K produces(22)
[CpMo(COhMe], the intermediate presumably found in the thermal substi-
tution reactions of [CpMo(COhMe]. Exchange of 13CO in [CpMo(COhr
is counterion dependent with the rates decreasing Lt > Na+ > PPN+,(23)
At 25C in THF the replacement of CO by PMe3 in [CpM(COhNO]
(M = Mo or W) to produce [CpM(CO)(NO)PMe3] follows a second-order
rate law: k (Mo) = 2.7 x to-I M-
1
S-I; k (W) = 4.5 x to-
2
M-
1
S-I.(24)
However, at low temperatures in PMe3 as solvent, complex 2 is produced,
which upon warming or PMe3 dilution converts to a 2: 1 mixture of
compounds 1 and 3. These observations and the rate law suggest Scheme
4 in which an intermediate is formed that contains either a bent nitrosyl
or 1/ 3 - C
5
H
5

Scheme 4

PMe
3
NO

,
,
1
M

M
ON/ I 'co

I I
co
1
2
M
ON/ I 'CO

3
The use of
17
0 nmr to study oxygen exchange between Hr 0 and
[Re(CO)6t in MeCN supports(2S) previous proposals of an acyl intermedi-
ate, [Re(CO)sCOOH]. The exchange rate is second order in H
2
0, probably
because a second water molecule functions as a base to accept a proton
from the water molecule attacking the carbonyl carbon.
Substitution of one or more CO ligands in [CpM(COhIJ (M = Mo
or W) by isonitriles, RNC, occurs quickly and in good yield in the presence
of catalytic amounts of the corresponding dimer [CpM(COhJ2 (M = Mo
or W). (26) It appears that the dimer dissociates into radicals in the initial
step. It is proposed(26) that these radicals then catalyze the substitution
reaction by both nonchain and chain pathways. In the nonchain mechanism,
[CpM(COhJ activates [CpM(COhIJ to nucleophilic attack by forming an
intermediate complex of unknown structure. A possible chain process is
Scheme 5
[CpM(COhh 2[CpM(COh]
fast
[CpM(COh] + RNC [CpM(COhRNC] + CO
[CpM(COhRNC] + [CpM(COhI] [CpM(COlz(RNC)I] + [CpM(COh]
shown in Scheme 5, where rapid substitution in the radical is followed by
iodine abstraction to give product.
[Fe(CO)sJ + nRNC -+ [Fe(CO)s-n(RNC)nJ + nCO (4)
[Fe(CO)5J + PR3 -+ [Fe(CO)4PR3J + CO (5)
Reactions (4) and (5) proceed cleanly in good-to-excellent yields in
reftuxing benzene or toluene in the presence of a cobalt(II) salt as a
catalyst.(27,28) For reaction (4) CoCh2H
2
0 was the catalyst precursor, and
the actual catalyst is postulated to be CoCh(RNC)n formed in situ. Neither
light nor radical inhibitors affect the reaction rate, and the mechanism is
thought to involve attack by catalyst at a carbonyl carbon, thus facilitating
its loss and replacement by RNC. Attack at the carbonyl oxygen is thought
unlikely because the good Lewis acid AlBr3 does not catalyze reaction (4),
and attack at the iron is discounted owing to the absence of anticipated
steric effects. However, the precise nature of the suggested catalyst -reactant
interaction is not elaborated. In reaction (5) PR
3
can be a variety of
phosphines and phosphites, and even AsPh
3
and SbPh
3
react. The active
catalyst is probably [CoX
2
(PR
3
hJ (X = Cl- or 1-). The reactivity order
10.1 Substitution Reactions
243
is: PPh
3
"" AsPh
3
"" P(OPh)3 > SbPh
3
> PMePh
2
> PMe2Ph > P(C6Hll h >
P(OEth > PBU3 > P(OMeh, This order is quite different from the usual
one for nucleophilic reactivity, and probably reflects steric and electronic
constraints imposed on the catalyst and on its equilibration with less reactive
species such as [CoX
2
(PR
3
hl As with reaction (4), the catalyst is suggested
to interact with the Fe-CO bond in some manner. Interestingly, catalysis
of reaction (5) is very solvent dependent, and does not occur in THF,
hexane, MeN0
2
, MeCN, CHCh, etc.
Reaction (5) is also catalyzed by [CpFe(COhh.(29) In this case the
catalyst is actually [Cp2Fe2(COhPR3l Reactivity follows the cone angle
of PR
3
, in contrast to the results with Co(II) catalysts. The rates are not
greatly affected by light or radical inhibitors. Replacement of CO in
[CpFe(COhI] by t-BuNC is also catalyzed by [CpFe(COhh.(30)
The rate of CO replacement in [Fe(CO)s] is many orders of magnitude
slower than in [Fe(COh(N4Me2)], reaction (6). A kinetic study with L
Me
1
N - N
(CO)l: 0 1 + L ---7 + CO (6)
'N - N
1
Me
consisting of a series of phosphines, phosphites, arsines, 4-cyanopyridine,
and t-BuNC shows that reaction (6) follows a strictly second-order rate
law.(31) No ligand-independent path is evident, in contrast to the thermal
reactions of [Fe(CO)s] and [Fe(CO)4L]. Both size (cone angle) and elec-
tronic factors (basicity and polarizability) are important. Very negative flSt
values, --146 J K-
I
mol-I, argue against chelate ring opening as an impor-
tant elementary step in the mechanism. Recognizing the known great
7T-acidity of the 1,4-dimethyltetraazabutadiene ligand, the proposed
mechanism assumes associative attack by nucleophile on the metal with
the N
4
Me
2
ligand accepting a pair of electrons in the transition state, shown
as complex 4. This kind of electron de localization allowing an associative
Me
I
/N-N
(CO)le II
I 'N-N
L I
Me
4
pathway to dominate is analogous to CO substitutions in complexes contain-
ing nitrosyl and 7T-hydrocarbon ligands. The rate of reaction (6) increases
with solvent polarity, and is especially rapid in alcohols, where the reason-
able suggestion is made(31) that hydrogen bonding lowers the transition
state energy as shown in complex 5. There is no evidence for hydrogen
bonding in the ground state with alcohols, but the strong Lewis acid BF3
coordinates in the ground state to give complex 6, and greatly accelerates
Me Me
I ,HOR
/N-N'
{CO)le II
I 'N - N,
L I "HOR
I /
BF
3
/N-N
(CO)le 0 I
'N-N
I 'BF
3
Me Me
5
6
the reaction rate, e.g., by a factor of 1.3 x 10
6
with PPh
3
as the nucleophile.
In contrast to the thermal reactions of [Fe(COh(N4Me2)], photosubstitution
of CO proceeds via a dissociative mechanism. (32)
[CpFe(COhMe] + L [CpFe(CO)(L)Me] + CO (7)
Photosubstitution of CO shown in equation (7) occurs with phosphines,
phosphites, and 13CO and has a quantum yield independent of the nature
or concentration of L. (33) Rate-determining CO dissociation from the
photoexcited reactant is indicated. Similar chemistry obtains with
[CpRu(COhMe], except that irradiation at 77 K allowed observation of
the [CpRu(CO)Me] intermediate. This was not possible with the iron
analog.
[Cp'Ru(COhBr] + L -. [Cp'Ru(CO)(L)Br] + CO (8)
(Cp' = CsHs, CsMe4Et; L = PPh3, P(OMeh, P(OPhh)
A study of reaction (8) in diglyme shows clearly the mechanism is
dissociative.(34) Surprisingly, the C
s
Me4Et complex dissociates CO about
18 times more rapidly than the CsHs analog. This result is ascribed to extra
stabilization of the transition state. Reaction (8) in BU20 follows a free
radical pathway and reproducible results are obtained only when a radical
inhibitor is present (duroquinone), in which case a D mechanism holds.
10.1.3. Replacement of Other Ligands in Mononuclear Metal
Complexes
245
Electrocatalysis of ligand substitution proceeding by a cationic chain
mechanism has been documented. (6,7) The application of a slight anodic
current through a MeCN solution of [(11
5
-C5H4Me)Mn(COhL] (L =
MeCN or py) and nucleophile L' (PPh
3
or t-BuNC) induces rapid ligand
substitution according to equation (9).(6) No reaction occurs in the absence
(9)
of the current. Table 10.1 gives some pertinent results. The very high
current efficiencies or turnover numbers show that the catalysis occurs with
very long kinetic chain lengths. The proposed mechanism, supported by
cyclic voltammetry studies, is given in Scheme 6. The homogeneous substi-
tution and electron transfer steps constitute a catalytic cycle initiated by
Scheme 6
MnL - e - --+ MnL + (initiation)
MnL + + L' -+ MnL'+ + L (substitution)
MnL'+ + MnL -+ MnL + + MnL' (electron transfer)
oxidation of a small amount of reactant [MnL]. The chain length depends
on the rate of the substitution reaction compared to the rate of decomposi-
tion of [MnLt by other pathways. The reduction potentials of the [MnL']
products in equation (9) are well positive of those of the [MnL] reactants,
thus ensuring that the electron transfer step in Scheme 6 has favorable
thermodynamics. Experimentally, the electrode potential is held near
Table 10.1. Electrocatalytic Substitution of L by L' in
[(T/s-CsHNe)Mn(CO)2L] at 22C in MeCN
a
L L'
MeCN PPh
3
MeCN t-BuNC
py PPh
3
a Data from Ref. 6.
Yield, %
100
95
96
Moles product per mole electrons passed.
Current efficiencyb
1013
365
260
enough to EO (MnL) to initiate the reaction, but well below EO (MnL').
The stable product is then neutral [MnL']. While [MnL'] may be formed
by homogeneous electron transfer (Scheme 6), [MnL't may also be reduced
directly at the electrode. The catalyzed substitution process in equation (9)
corresponds to an electrochemical ECE or SON2 mechanism.
Electrocatalytic substitution initiated by oxidation occurs with Group
VI metal carbonyl derivatives. (7) Several of the reactions studied, and ones
which give little or no product when uncatalyzed, are shown in equations
!ac-[(MeCNhW(COh] !ac-[(t-BuNChW(COh] (10)
cis-[(py)zMo(COL] cis-[(BuNC)zMo(CO)4] (11)
cis-[(MeCN)zW(CO)4] cis-[(MeCN)(PPh
3
)W(CO)4] (12)
(10)-(12). The mechanism described above for the reactions of [1/s-
(C
s
H
4
Me)Mn(CO)zL] applies to these reactions. The success of elec-
trocatalysis of ligand substitution initiated by oxidation depends on the
stabilities of the cationic radicals produced and in most cases will not be
practical unless EO of the product is more positive than EO of the reactant.
This latter restriction is a serious one, for many ligand substitutions at
metal centers, including CO replacements, will not meet this requirement.
The best chance of success comes when the incoming ligand is a better 1T
acid than the one being replaced. Electrocatalysis initiated by reduction,
however, does not have this problem (see below and Section 10.1.4).
The actual mechanism of ligand substitution in the 17 -electron cationic
radicals produced during the electro catalysis (e.g., Scheme 6) has yet to
be addressed, although guesses(6,7) that associative pathways dominate have
been made. Photo substitution of MeCN in [(MeCN)(phen)Re(COht by
PPh
3
or py is closely related to the reactions just described. (5) The quantum
yields are considerably greater than 1, and this photocatalysis is proposed
to follow a radical chain mechanism, Scheme 7. Excited state electron
transfer from quencher Q (PPh
3
) generates the labile 19-electron species
[(MeCN)Re] which reacts with nucleophile L in a chain process, Confirma-
Scheme 7
[(MeCN)Ret + hll -+ [(MeCN)Re*t [(MeCN)Re] + Q+
[(MeCN)Re] + L -+ [LRe] + MeCN
[LRe] + [(MeCN)Ret -+ [LRet + [(MeCN)Re]
tion of this scheme comes from the observation(5) of very similar electro-
catalysis of MeCN substitution when the radical [(MeCN)Rej is generated
in the presence of nucleophile by controlled potential reduction of
[(MeCN)Ret.
An SH2 mechanism is reported(35) for the displacement of alkyl radicals
from alkyl zirconocenes by di-t-butyl nitroxide. Substitution in vanadium
carbonyls in THF solution according to equation (13) follows a D mechan-
ism and is weakly counterion dependent in the order Na+ > Et
4
N+.(36)
[V(CO)sPR
3
r + P(OPhh ...... [V(CO)sp(OPhhr + PR
3
(R = Ph or Bu) (13)
Ligand substitution reactions of Group VI metal pentacarbonyl
piperidine complexes, equation (14), is catalyzed by the Lewis bases THF
[M(CO)s(pip)] + PR
3
...... [M(CO)sPR
3
] + pip
(14)
and BU3PO.(37) Infrared evidence shows that the Lewis bases hydrogen-
bond to the piperidine N - H. Equilibrium constants for this association
calculated from static ir data and from curvature in plots of kobs versus
nucleophile concentration agree reasonably well. The catalyzed substitution
pathway is shown in Scheme 8. This mechanism is best described as
Scheme 8
K,
M-NHR2 + OPBU3 M-NR2HOPBu3
M-NR2HOPBu3 M-OPBu3 + NHR2
dissociative interchange (I
d
). An alternative scheme in which [M-NHR
2
]
and OPBU3 react directly and Kc represents a dead-end equilibrium is not
supported by the activation parameters or the metal dependence of the
rate constants. The nonreacting ligand L in equation (15) exerts a large
cis-[Mo(CO)4(L)(pip)] + CO ...... [M(CO)sL] + pip (15)
effect on the dissociative loss of piperidine in heptane solvent. (38) The
relative rates at 40C are: L = PPh
3
(168) > PMe2Ph(12.6) >
P(OMeh(2.04) > CO(1.00). This series correlates well with steric factors.
The intermediate [Cr(CO)4PPh
3
] formed during the dissociative substitu-
tion of PPh
3
in reaction (16) rearranges (C
4v
-+ C.) faster than CO addition
can occur. (39)
trans-[Cr(CO)4(PPh
3
h] + 13CO -+ cis-[Cr(CO)4e
3
CO)PPh
3
] + PPh
3
(16)
Displacement of olefin from a Group VI metal as in equation (17)
follows a strictly D mechanism in dichloroethane. (40) The nonreacting ligand
cis-[M(COML)(olefin)] + P(OU-Pr)h -+
cis-[M(COML)P(OU-Pr)h] + olefin (17)
L exerts a large effect on the rate, approximately determined by its steric
requirements: L = PEt3 < PU-Pr)Ph2 < PU-PrhPh < PPh
3
< PU-Prh. The
rate of dissociation of olefin is: maleic anhydride dimethyl fumarate <
bis(trimethylsilyl)fumarate < dimethyl maleate < ethylene. The most inter-
esting aspect of this study is the reactivity order W Mo Cr. Normally
Mo is the most reactive Group VI metal, and the unusual results for reaction
(17) are reasonably ascribed to steric acceleration with Cr due to the
presence of ligand L.
( co
(
s " I ..... CO
Cr
S /' I 'CO
) co
7
Trialkyl phosphites displace 3,6-dithiaoctane from complex (7) by the
usual chelate ring opening mechanism with k2 k
3
[L], equations (18) and
(19).(41) An earlier study of the same reaction with complex 8 gave the
s
/) k. k3
M M -S-S ----t+ ML2 + S-S
" k2
(18)
S
k _ k1k3[L]
obs - k2 + k
3
[L]
(19)
unusual result that k2 :::::: k
3
[L]. An X-ray structure of 8 shows steric distor-
tion from octahedral symmetry that is not present in 7. Accordingly, it
+ CO
(
s ........ I ",CO
Cr
/ I 'CO
S CO
-l-
I
8
249
seems that complex 8 has an unusually small value for k2 owing to a steric
barrier in the ring closure step.
The reaction of [Mo(CO)4(bipy)] with CN- produces(42) [Mo(COk
(CNhf-. In various solvents the observed rate constant is kobs =
kl + k
2
[CN-]. The kl term refers to a solvolysis pathway. Reaction of
[Mo(CO)4(5-N0
2
phen)] and CN- goes through a Meisenheimer adduct
and two kinetically distinct stages are seen, the first dependent and the
second independent of [CN-]. The second stage presumably is the
intramolecular transfer of CN- from the 5-N0
2
phen ring to the metal.
Both thermal and photochemical substitution of PhCN by MeCN in
[Cp
2
Mo(I)(NCPh)t occurs by a dissociative mechanism.(43) Anation and
acid-induced cleavage of Cr(III) alkyl complexes has been reported.(44-46)
Iodide abstraction with AgBF4 from [CpFe(COhI] (FpI) in CH
2
Ch
and CHCh proceeds in two stages. (47) First, the FpI is entirely converted
to Fp2I+, BFi which reacts in a second step to give FpBF4. Reaction of
the 1/ 4 -heterodiene complex 9 with diphos to yield 10 according to equation
(20) follows a mixed AID mechanism shown in Scheme 9.(48) In toluene

diphos
DC, /P:)
) Fe- P
/Fe
(P-P) Dc/I
(20)
DC I' PPh
3
p.--..p
CO
9 10
solvent the activation parameters are k
l
: /1H* = 127 kJ mol-I; !J.S* =
71 J K-
1
mol-I; ka: /1H* = 85 kJ mol-I; !J.S* = -46 J K-
1
mol-I.
Although an associative mechanism for reaction (21) would not be
surprising, a kinetic study(49) clearly establishes a D mechanism in DMSO
and dichloroethane.
(X = CI- or Br) (21)
250

....
OC/I'PPh
CO 3

10 Substitution and Insertion Reactions
Scheme 9

1
Fe
oc/I "PPh
3
CO
fast
10
At 35C, PMe
2
Ph (L) simply replaces the ethylene in complex 11, but
at 6C the product is 12. (50) The mechanism of formation of 12 is suggested
L L
+
CI" 1 / CI L"I / CI
Ru CH
2
Ru
OC/I ........... 11 OC / 1 "CH
2
CH
2
L
L CH
2
L
11 12
to involve initial nucleophilic attack at the coordinated olefin followed by
loss of Cl- trans to the CH
z
CH
2
L group. Another example of ligand
substitution reactivity being greatly affected by initial nucleophilic attack
on a coordinated ligand is provided by a kinetic study of the reaction shown
in Scheme 10(51) [L = PMezPh; L' = P(OMeh]' In this case reaction by a
classical dissociative mechanism does not occur; complex 13 and L' do not
react in the absence of excess ligand L.
A kinetic study of PPh
3
substitution into polymer-supported
[RuCh(NO)(SbPh
3
hJ has appeared.(5Z)
Although phosphine substitution reactions of [CpM(COh] (M = Co
or Rh) have long been known to be associative, the substitution in equation
(22) has been shown to agree quantitatively with a dissociative mechan-
ism.(53) An associative mechanism was anticipated because the linear inter-
+ L ,
13
Scheme 10
,
L +

Ru H
's
L
14
L +
L,...I /SX
H
Ru
'S L
+ L
251
+ L
mediate [CpCoL] is forced by symmetry to have a triplet ground state. It
is concluded that either the intermediate is bent or the large activation
barrier expected for a spin change is not operative in this case.
[CpCo(PPh3h] + PMe3 [CpCo(PPh
3
)(PMe3)] + PPh
3
(22)
Rapid exchange of solvent (S) in complex 15 (M = Rh or Ir) occurs
by a D mechanism.(54) Table 10.2 shows that Rh Ir, as expected. Solvent
exchange is much faster than classical substitution reactions. This is ascribed
to the trans effect of the hydride ligand.
PR3 +
I/S
H-M-S
H/I
PR
3
15
The rate of arene exchange in [(arene)Ir(COD)t in acetone solvent
is independent of the incoming arene concentration and goes through an
observable intermediate, designated [(acetone)xIr(COD)t.(55) The rate
252
Table 10.2. Solvent Exchange in Complexes 15 at 25C
a
M s
Ir PPh3 Me2CO 395 7 67.3 0.7 30.4 2.3
Ir PPh3
MeCN (3.34 0.46) x 10-
3
95.6 2.3 2B.2 7.1
Ir P(C
6
H
ll
h MeCN 1.05 0.03 BO.3 0.4 24.7 1.2
Rh PPh3 Me2CO (1.95 0.27) x 10
4
57.6 1.6 30.4 6.5
Rh PPh3 MeCN 10.24 0.13 76.7 0.6 31.71.B
Rh P(C6Hll h MeCN 552 43 59.9 2.6 B.3 9.0
a Data from Ref. 54.
depends on the bound arene in the expected order: toluene> p-xylene >
mesitylene.
The nickel(I) complex [CpNiL
2
] (L = PR
3
), disproportionates rapidly
on the cyclic voltammetry time scale [equation (23)].(56) The [CpNiL
2
]
complexes are suggested to be likely intermediates in the reaction of
nickelocene with phosphorous ligands (L) to give [NiL4] and ClOH
lO
.
2[CpNiL
2
] -... [NiL4] + [Cp2Ni] (23)
Dissociation of alkynes from the five-coordinate complexes
[(bipy)pt(Me)(X)(R
2
C
2
)] (X = Cl- or r; R = C0
2
Me or CF
3
) has been
reported. (57) For R = C0
2
Me the rate is strongly accelerated in polar
solvents, and a mechanism involving initial halide dissociation is proposed.
For R = CF
3
, the mechanism seems to be simple rate-determining alkyne
dissociation with no halide loss. Based on synthetic and stereochemical
studies, the five-coordinate ethylene complexes 16 (X = halide; N - N =
RNCHCHNR or RNHCH
2
CH
2
NHR) are proposed to exchange X- by
initial dissociation of X-, and to exchange olefin or N - N ligands by initial
opening of the chelate ring to give a [Pt-N-N] intermediate.(58)
X

I
X
16
10.1.4. Substitution Reactions of Polynuclear Metal Complexes
Electrocatalysis of nucleophilic substitution in the cluster compounds
[(Ph2C2)C02(CO)6J and [(YC)C03 (CO)9J (Y = Ph or Cl) is reported to be
initiated by reduction.(4) The radical anions of these species very rapidly
substitute a phosphine for CO. The product is then spontaneously oxidized
to the neutral substituted cluster because EO of the product is cathodic to
EO of reactant. The net effect is an ECE mechanism. Thermal substitution
in the absence of reduction is very slow. These remarkable reactions promise
to have important implications for synthesis in metal cluster chemistry.
Scheme 11 illustrates the proposed mechanism. The electron added to
complex 17 goes into a metal-metal antibonding orbital. This leads to
reversible metal-metal bond cleavage to give the intermediate 18, which
contains a 17 -electron metal center that rapidly substitutes a CO, probably
by an associative mechanism, and is then oxidized to reform the metal-metal
bond to give 19. The oxidation can be by electron transfer to the electrode
17
+L
)
Scheme 11
R R
" C /
C-...
I
(CO)3CO - CO(CO)2L
19
18
or to reactant 17. In either case the overall reaction is catalytic. Application
of this technique to a variety of metal clusters has already appeared. (59)
Addition of catalytic amounts of Ph
2
CO- to a mixture of cluster and
stoichiometric amount of nucleophile in THF gives greatly improved yields
of [Fe3(CO)l1L], [RU3(COh2-"L,,], [Os3(CO)uL], and [H4Ru4(COh2-"L,,]
for L = PR
3
, P(ORh, and t-BuNC. Scheme 12 shows the reaction of
[RU3(COh2] to give monosubstituted product. The di- and trisubstituted
product is readily obtained by adjusting the amount of nucleophile. The
Scheme 12
[RU3(COh2] + Ph2CO- --+ [RU3(COh2r + Ph2CO
[RU3(COh2r + L --+ [RU3(CO)l1Lr + CO
[RU3(CO)l1Lr + [RU3(COh2] --+ [RU3(CO)l1L] + [RU3(COh2r
simple non catalytic thermal reaction gives only trisubstituted product. The
success of these cluster substitution reactions requires that the radical anion
be stable long enough to react with nucleophile before fragmentation
occurs, and that the incoming ligand be a weaker 1T' acid than CO so that
electron transfer back to reactant is favored. The electrocatalytic chain
mechanism has also been applied to the facile synthesis of stereoisomers
of [(CF
3
)6C
6
C0
2
(COh(P(OMehh].(60)
An activation enthalpy of 135.9 2.2 kJ mol-
1
is required for the
homolytic fission of the Mo-Mo bond in the decomposition reaction of
[Cp2M02(CO)6] with oxygen.(61) Replacement of two CO ligands by
diphenylacetylene in [Cp2M02(CO)6] involves successive loss of two CO's
prior to reaction with C
2
Ph
2
.(62) Homolytic Mo-Mo bond fission is com-
pletely reversible, but does not lead to any product.
Replacement of PEt
3
by PMe2Ph or PMe3 in complex 20 occurs rapidly
at room temperature in toluene. (63) All four PEt3ligands can be substituted,
P Me
I/Me I/p
M6 iiiiiiiiEiiiE Me)
Me/I p/I
P Me
20
and each replacement follows a D mechanism even though vacant axial
sites are available. For the first substitution with PMe2Ph, !lJ[t =
86 kJ mol-
1
; !:J.S
t
= 82 J K-
1
mol-
1
. The driving force in these reactions is
proposed to be relief of steric congestion as PEt
3
departs.
Flash photolysis of [M
2
(COho] (M = Mn or Re) in hexane at 22C
under an atmosphere of CO generates the [M(COh] radicals that rapidly
recombine with rate constants k(Mn) = 9.5 x 10
8
M-
1
S-1; k(Re) =
3.7 x 10
9
M-
1
S-1.(64) Under an inert atmosphere photolysis leads to more
complex behavior with intermediates [Mz(CO)s] and [M
2
(CO)9] postulated
to form via loss of CO from [M(CO)s]. Computer modeling of a reaction
scheme having CO dissociate from [M(COh] with a rate constant of
-100 s -1 gives only moderate agreement with experiment. The greater
reactivity of [Re(CO)s] compared to [Mn(CO)s] is shown by a pulse radioly-
sis study of reaction (24) in ethanol at 22C: k(Mn) = 6.1 x 105 M-
I
S-I;
k(Re) = 3.9 x 10
7
M-
I
S-I.(65)
[M(CO)s] + CCl
4
-+ [M(CO)sCI] + CCh (24)
That 17 -electron organometallic radicals are labile to ligand substitu-
tion is well established. However, the mechanism of these reactions is less
well understood. Brown(64,66,67) has argued that [M(CO)s] (M = Mn or
Re) reacts by a dissociative pathway. More recently Brown found(68) that
[Mn(COhL
2
] + CO -+ [M(CO)4L]+ L
[L = PBU3 or P(i-Buh] (25)
reaction (25) follows an associative mechanism in hexane at 20C, and
suggests that there may be a transition in the prevalent pathway for
substitution, from dissociative for [Mn(CO)s] to associative for
[Mn(COhL
2
]. Based on competition studies of chlorine abstraction and
substitution reactions of [Re(CO)s] generated by photolysis in
POe(69) has convincingly demonstrated that phosphine substitution into
[Re(CO)s] is associative. Poe has discussed(70) the evidence for his sugges-
tion that most 17 -electron organometallic radicals, including [M( CO)s]
(M = Mn or Re), substitute ligands via associative pathways.
Replacement of CO by a phosphine in the 17 -electron species [V (CO )6]
according to equation (26) is first order in PR
3
. (71) At 25C for PPh
3
,
[V(CO)6] + PR
3
hexane. [V(CO)sPR
3
] + CO (26)
k = 2.5 X 10-
1
M-
1
S-I; aH* = 42 2 kJ mol-I; as* = -116
7 J K-
I
mol-I. The better nucleophile PBU3 reacts about 200 times faster
than PPh
3
. These data clearly indicate an associative mechanism.
Whether or not the M-M bond ruptures during the thermal substitu-
tion reactions of [M
2
(COho] (M = Mn or Re) is a question that continues
to stimulate publications. Atwood(72) argued that phosphorus nucleophile
substitution into [ReMn(COho] involves rate-limiting CO dissociation and
not Re-Mn cleavage. Poe(73) argues for M-M cleavage based on similar
rates for substitution and oxidative decomposition, and on the fact that
the latter reaction shows a fractional order in the metal dimer. Atwood(74)
suggests that the fractional order may be due to peroxides in the solvent
(decalin), and observes that substitutions into [ReMn(COho] give no
homodimetallic products as might be expected for a Re-Mn fission mechan-
ism. Crossover experiments by Basolo(75) provide strong evidence that
reactions of [Re2(COho] and [ReMn(COho] do not involve homolytic bond
cleavage. Thus, a mixture of [Mn2(COho] and [Re2(COho] held at 130C
for 92 h gave no [ReMn(COho] even though substitution of PPh
3
into
[Re2(COho] readily occurs under these conditions. It is expected that the
Mn-Mn bond would cleave more easily than Re-Re, and therefore the
conclusion is that substitution in [Re2(COho] occurs via CO loss. Similar
experiments with [ReMn(COho] and PPh
3
give substitution for CO but no
homodimetallic species. It was verified that failure to observe metal scram-
bling is not due to unfavorable thermodynamics. The authors note, however,
that metal-metal bond cleavage in the reactions of [Mn2(COho] cannot be
ruled out at this time, and that metal-metal cleavage may become important
with [Re2(COho] and [ReMn(COho] at temperatures > 140C.
The kinetics of Fe-Co bond cleavage by a series of P-, As-, and Sb-
donor ligands as shown in equation (27) are first order in nucleophile.(76)
Me
I
) (CO)le- As - CO(CO)3L
L
I
Me
(27)
The modest variation of k2 with nucleophile suggests an interchange
mechanism, fd for the weaker nucleophiles becoming more fa with the
more reactive bases.
Replacement of CO by PPh3 in [H2FeRu3(CO)uJ follows a
nucleophile-independent rate-limiting CO dissociation mechanism with
Mit = 106 4 kJ mol-
1
and aS
t
= 20 13 J K-
1
mol-
1
in hexane sol-
vent.(77) Photolysis of [H2FeRu3(CO) 13], [H
2
Ru4(CO) 13], and
[H
2
FeOs3(CO)13] in the presence of PPh
3
gives photosubstitution of PPh
3
for CO with moderate efficiency.(78) The quantum yield is independent of
PPh
3
concentration. The kinetic data cannot distinguish between CO dis-
sociation or metal-metal cleavage in the primary photochemical event.
However, the lack of significant cluster fragmentation in the presence of
CO and the expectation that a metal-metal bond rupture mechanism would
give a dependence of the quantum yield on the PPh
3
concentration are
more consistent with CO dissociation.
The metal-metal bond in [(PEt
3
h(CO)RhCo(CO)4] is polar and best
described as a planar Rh(I) complex containing a [CO(CO)4r ligand.(79) A
kinetic study of equation (28) in THF at 20C, gives k1 = 1.7 X 10
4
M-
1
S-1
and k-1 = 5.1 X 10
6
M-
1
S -1. An associative mechanism typical of substitu-
tions at planar d
8
complexes is proposed.
k
[(PEt3h(CO)Rh-Co(CO)4J + MeCN ......,.2
k "1
[(PEt
3
h(CO)Rh(MeCN)t + [CO(CO)4r (28)
The kinetics of fragmentation of [C0
4
(CO)g(PPh
3
)4] in dichloroethane
to give [C0
2
(COMPPh
3
h] is claimed to proceed by three pathways that
involve PPh
3
dissociation, CO dissociation, and spontaneous activation
without loss or gain of ligands. (80)
Attempts have been made to separate steric and electronic factors
governing ligand substitution in tetranuclear clusters of cobalt and iridium.
For a series of isostructural complexes [C0
4
(CO)l1L], the rate of dissociative
loss of CO has been determined by measuring 13CO exchange rates.(81)
The ligand L is a phosphine or phosphite, and occupies an axial position
as shown in structure 21. The relative rates of CO-dissociation in heptane
21
at 40C are L = PEh(4.8) > P(OEth(1.1)"." CO(1.0). The similar rate for
the two ligands of similar spacial requirement and the acceleration with
the larger PEh ligand suggest that steric factors dominate in these reactions.
The relative order of reactivity for dissociative CO loss in [C0
4
(CO)12] with
progressive substitution by P(OMeh, is given in equation (29).(81.82) Thus,
[C0
4
(CO)u] [C0
4
(CO)l1P(OMeh] [C0
4
(COho(P(Mehh]
(29)
successive replacement by the small1T-acceptor P(OMeh has little effect.
This contrasts sharply with the [Ir4(CO)12] system where substitution of
CO by PPh3 causes large rate enhancements of dissociative CO loss
[equation (30)].(83) This rate acceleration has been taken as evidence that
[Ir4(CO)12] [Ir4(CO)l1PPh3] [Ir4(COho(PPh
3
h]
(30)
electronic interactions can be transmitted among metal atoms in a cluster
and thereby indicate a kind of cooperative effect that may be important
Table 10.3. Rate Constants for co
Dissociation from [Ir4(COMPR3)3] at
80
D
C in Tetrachloroethylene
a
R
10
3
kjs-l (Jbjdeg
Me 0.173 118
Et 1.33 132
Bu 1.27 132
i-Pr 6.76 160
Ph 7.84 145
a From Ref. 84.
b Tolman cone angle.
in catalysis. However, it has recently been proposed(81.84) that the major
part of this behavior is steric and not electronic. Dissociative CO exchange
rates of [Ir4(COMPR3h] in tetrachloroethylene at 30C are given in Table
10.3.(84) All of the [Ir4(COMPR3h] complexes are isostructional(84) with
each Ir atom in the basal plane containing one PR
3
ligand, two of which
are probably equatorial and one axial (see structure 21). It follows that
reactivity variations do not merely reflect structural changes. CO dissoci-
ation in [Ir4(COMPR3h] is labilized relative to [Ir4(CO)d and depends
on the phosphine in the following way: PPh
3
(78,400) > P(i-Prh (45,100) >
PEh (8870) PBU3 (8470) > PMe3 (1150). The CO labilization depends
strongly on the size of PR
3
and only weakly on its basicity. Analogous
steric acceleration of phosphine dissociation from [Ir4(CO)g(PR3)4] has
been observed.(84,85) PEt3 dissociates 3300 times faster than PMe3 in spite
of their similar basicity.
The kinetics of CO displacement by t-BuNC in [Ir
4
(CO)12] to give
[Ir4(COh2-n (t-BuNC)n] show a strictly associative mechanism for substitu-
tion of up to four CO ligands. (86) The relative rates are not greatly dependent
on the degree of substitution, 1: 3 : 3 : 0.5 for n ranging from 1 to 4. This
contrasts with CO substitution with PPh
3
, which shows a progressively
more important dissociative pathway as the substitution increases, and
which occurs many orders of magnitude more slowly than the t-BuNC
reactions. This striking difference in behavior is ascribed to steric effects, (86)
although structural changes may be important here since the t-BuNC
derivatives adopt the [Ir4(COh2] structure, i.e., have only terminal car-
bonyls.
Reaction (31) follows a two-term rate law, equation (32), with the k 1
term nucleophile independent and presumably due to CO dissociation. (87)
The dependence of k2 on the nucleophile is large, the relative reactivities
10.2 Insertion Reactions
[Ir4(CO)d + L -+ [Ir4(CO)l1L] + CO
(L = PBU3, PPh3, P(OPhh, or AsPh
3
)
kobs = kl + k2[L]
259
(31)
(32)
being PBU3 (120) > P(OPhh (2.8) > PPh
3
(1.0) > AsPh
3
(0.19). The k2
term is assigned to direct nucleophilic attack on iridium. A steric contribu-
tion is also present since PPh3 is less reactive than P(OPhh. Substitution
into [Ir4(CO)l1L] also follows the rate law in equation (32), but the k2
term is small.(88) The relative dependence of kl on the group L is PBU3
(180) > PPh
3
(90) > AsPh
3
(50) > P(OPhh (8) > CO (1). This order is
suggested to reflect cis labilization of CO much as seen with mononuclear
complexes and to be predominantly an electronic effect operating to stabil-
ize the transition state. (88) The CO is proposed to dissociate from the
substituted iridium and the unsaturation is then transferred to another
metal site via a bridging carbonyl. An analogous study of substitution into
[Ir4(COhoL2] again shows a predominantly dissociative mechanism.(89) The
dependence of kl on L is AsPh
3
(1200) = PPh
3
(1200) > PBU3 (54) >
P(OPhh (21) > CO (1), and is somewhat different from that with
[Ir4(CO)l1L]. The authors argue that the primary effect of L is to labilize
a CO bound to the same metal and that this occurs via transition state
stabilization as with [Ir4(CO)l1L]. Steric effects are suggested to playa
minor role in the acceleration of CO dissociation from these iridium
clusters. (89)
Obviously there are conflicting views about the relative importance of
electronic and steric effects in the substitution reactions of [Ir4(COh2-nLn].
This reviewer finds the arguments in favor of substantial steric effects to
be convincing.
10.2. Insertion Reactions
10.2.1. Carbon Monoxide Insertion
The effect of substituents (X) on the rate of benzyl group migration
according to equation (33) has been studied.(90) In CH
3
CN solvent at high
[CpMo(COhCH2C6H4X] + PPh
3
-+
trans-[CpMo(COh(PPh
3
)(COCH
2
C
6
H
4
X)] (33)
PPh3 concentrations a limiting rate is reached that presumably represents
rate-determining benzyl migration to give the usual acyl type intermediate
that is then trapped by nucleophile. The limiting rate constant increases
with the electron-releasing character of X. A correlation to Hammett (T
parameters exists, with a slope p = -0.97. In DMSO solvent reaction (33)
is much faster and there is some evidence for initial formation of a cis
product that isomerizes to trans. Solvent assistance in the rate-determining
migration step is proposed to account for the approximately 15-fold increase
in limiting rate in DMSO compared to MeCN. Solvent effects in CO
insertion reactions are well known to be substantial. A recent attempt to
more clearly define the role of solvent involves reaction (34). (91) The rate
data fit equation (35) and the proposed mechanism is given in Scheme 13.
[CpMo(COhMe] + PMePh
2
--+ [CpMe(COh(PMePh
2
)COMe] (34)
k = k
1
k
2
[PMePh
2
] + k [PM Ph ]
obs k-l + k
2
[PMePh
2
] 3 e 2
Scheme 13
+ s
"
,
(CO)3Mo- Me
(35)
[$>
(CO) 2Mo - COMe
I
S
Table 10.4 gives the rate constants. The magnitude of k3 is almost indepen-
dent of solvent as might be expected for direct nucleophilic attack. Although
the solvent polarity does not change much, there is a large variation in
donicity due to steric blocking with 2-MeTHF and 2,S-Me2 THF. Therefore,
if the role of solvent in alkyl migrations were to stabilize the acyl intermedi-
ate by simple electrostatic interactions, k 1 would not be expected to vary
appreciably. The large variation and its correlation to donicity seen in
Table 10.4. Rate Constants for Scheme 13 at
59. 9C a
Solvent (S)
THF
3-MeTHF
2-MeTHF
2,5-Me2THF
a Data from Ref. 91.
7.78 0.07
6.46 0.05
1.48 0.05
0.23 0.03
1.73 0.08
1.86 0.08
1.95 0.12
1.67 0.07
261
Table lOA is proposed to imply direct attack (coordination) of solvent at
the metal center during the migration step.(91)
Both 12CO and P(OCH
2
hCMe have been used to induce CO insertion
in cis-[MeMn(CO)4e
3
CO)].(92) In THF/acetone at 25C an analysis of the
13CO positional isomers in the products shows that migration proceeds
through a square-base pyramid with a basal acetyl group as shown in
complex 22. Solvent may also be coordinated and/or the acetyl group may
CO
I /CO
OC-M-COMe
OC / :
S
22
exhibit 17
2
bonding through the carbonyl oxygen. In HMPA, however,
12CO-induced insertion gives complete label randomization, possibly
because HMPA coordinates to the intermediate 22 and increases its lifetime
so that interconversions can occur prior to nucleophile addition. Bases
more nucleophilic than CO give a normal product distribution in HMP A.
Lewis acids such as AIX
3
are known to induce rapid alkyl migration
in metal carbonyls. (93) Equation (36) shows the product formed in the
absence of nucleophile. Subatmospheric CO converts 23 to
[Mn(COhCOMeAIX
3
]. Comparison of the rate of reaction (36) to the
.)
/Me
(CO)4Mn - C
I \
X 0 (36)
\. /
AIX
2
23
262
un catalyzed migration shows that AIX
3
(X = CI- or Br -) induces a rate
acceleration of _10
8
.(94) This is taken as strong evidence that AIX
3
directly
assists the migration and does not merely function to trap the unsaturated
acyl intermediate. The AIX
3
probably rapidly coordinates to a carbonyl
oxygen and increases the electrophilicity of the carbonyl carbon as suggested
10 equation (37). Protonic acids also accelerate methyl migration in
fast

..--
Me
I
(CO)4Mn-CO-AIX3 -+ 23 (37)
[MeMn(CO)s].(9S) With CF
3
COOH, CChHCOOH, and CClH
2
COOH the
rate enhancements are 9.4, 7.2, and 2.4 at 2BoC in toluene under Pea =
374 torr. The catalysis follows the acid pKa, although for strong acids
Mn-Me cleavage to give CH
4
becomes the major reaction. There is no
evidence that protonic acids hydrogen-bond to the acyl intermediate as
AIX
3
does in structure 23, but there is evidence that the product
[Mn(CO)sCOMe] is stabilized by hydrogen bonding. It is suggested that
the protonic acids function by hydrogen bonding to a carbonyl oxygen in
the transition state. Although they function as catalysts, protonic acids are
far less effective than AIX
3
.
Several other examples of CO insertions induced by electrophilic
reagents have appeared. Formation of the hydroxy carbene in equation
(38) is promoted by HCl. (96)
L L
OC, 1 /CI
HCI
OC,I/CI
Os
)
Os
(38)
OC / 1 'Et (L = PPh
3
)
Et
- C / 1 'CI
L 1 L
HO
The cationic complexes [CpFe(COht and [CpMo(Coht induce
methyl migration in [CpFe(COhMe] and [CpM(COhMe] (M = Mo or
W).(97)
CO insertions in [CpFe(COhR] usually require a very high concentra-
tion of nucleophile for a limiting rate to be reached. This makes it difficult
to determine the value of k t, the rate constant for migration of R to give
the unsaturated acyl intermediate. However, in DMSO the intermediate
is stabilized by solvent coordination and can be characterized. (98) This
enables a separate kinetic study of reactions (39) and (40).(99) Changing R
is found to cause a large variation in kt, consistent with the usual mechanism
involving considerable Fe-C bond breaking in the transition state. The
order of kl is (Me3SihCH Me3CCH2 > s-Bu > i-Pr > Me3SiCH2 >
CyCH2> i-Bu > Et > Pr "" C6H13 > Me. Both steric and electronic factors
10.2 Insertion Reactions 263
k
[CpFe(COhR] + DMSO [CpFe(CO)(COR)(DMSO)] (39)
L,
[CpFe(CO)(COR)(DMSO) + PPh3
[CpFe(CO)(COR)PPh
3
)] + DMSO (40)
are important, with the former somewhat more important. The equilibrium
constants for reaction (39) follow the same trend. L1 and k2 are much
less dependent on R than is k
1

Cp
CP CP
I
I
I
..... Fe
,Fe, * ,Fe, *
OC l' p*
OC 1 P
" 1 P ,
Me
h
C
,
O=C
0:7 Me
'Me
24 2S 26
Carbonylation of complex 24 where p* is (S)-PPh
2
NCH
3
CHCH
3
Ph
gives the acyl complex 25 with a stereo selectivity of more than 90%. (100.101)
This result is not compatible with methyl migration, but rather with "CO
migration" to give the 1J2-acetyl intermediate 26. However, the
stereochemistry of reaction (41) is consistent with methyl migrationy02)
AgBF4
[CpRh(I)(COMe)(L *)] [CpRh(CO)(Me)(L *)t
Na!
[L * = (S)-PPh
2
NHCHMePh] (41)
Interestingly, [CpRh(Me)(L *)(1)] epimerizes rapidly when treated with
AgBF4 and then NaI in acetone. It follows that the configuration at the
rhodium is maintained only when an acyl group is present in the unsaturated
intermediate. It is suggested that this is due to the ability of the acyl group
in [CpRh(COMe)L *] to decarbonylate temporarily and fill the open coordi-
nation site.
A report of Lewis-base-induced CO insertion reactions of fac-
[(diars)Fe(COhMet has appeared.(103)
Reaction (42) is the first example of methyl migration that is rapid on
the nmr time scale at room temperatureY04) Both k1 and k-1 must be of
the order of 10
2
_10
3
S-l and are 10
7
_10
8
times greater than CO insertion
in [MeMn(CO)s]. An X-ray structure of 27 shows that the chloride is
COMe + CO +
L,...I ..........
L
kl L,I .......... L
Rh , ' Rh
CI""""" 'L k_l Me""""" I 'L
(42)
27
CI
264
distorted somewhat towards the vacant axial site in the square pyramid.
This and the positive charge on the complex are suggested to account for
the large rate constants.
Insertion of CO in complexes of Pt(II) is sometimes accelerated by
the presence of SnCh. A study to investigate the role of tin chloride has
appeared. (lOS) In chloroform under CO, complex 28 is rapidly converted
to the ionic product 29 by dissociation of SnCI). In the absence of CO,
complex 29 is attacked by the SnC13 to give a five-coordinate intermediate
that inserts CO to give the final product 30. With excess CO, 29 also
trans-[Pt(SnCh)(C6Hs)(PPh3hJ
28
trans-[Pt(CO)(C
6
H
s
)(PPh
3
ht + SnCI)
29
-----+ trans-[Pt(SnCh)(COC6Hs)(PPh3hJ (43)
30
converts to 30 but a mechanism involving dissociation of PPh
3
contributes.
The role of SnCI) in carbonylation and decarbonylation seems to be related
to its facile dissociation and its ability to attack intermediates to give
complexes that can undergo insertion. Insertion as shown in equation (44)
K
,
2
,
(44)
has been studied as a function of R.(106) Table 10.5 shows that K varies
from zero to very large, suggesting that electronic changes in R can have
at least as great an effect as variation of the neutral ligand L or the anionic
Table 10.5. Equilibrium Constants at 38C for co Insertion
in Equation (44) a
R K R K
p-C6H4NMe2
00 p-C
6
H
4
CJ 20
p-C
6
H
4
OMe 2170 m-C
6
H
4
Cl 3.3
p-C
6
H4Me 360 p-C
6
H
4
OCOMe 3.3
m-C6H4Me 140 p-C
6
H
4
CN 0
C6H5
100 o-C6H4Me 0
m-C
6
H4OMe 70 o-C6H
4
OMe 9
a Solvent CDCl, . From Ref. 106.
ligand. Electron-releasing groups in R increase and electron-withdrawing
groups decrease K.
The two-electron reduction of [Fe2(CO)6(PPh2h] ruptures the Fe-Fe
\;lond to give a stable dianion 31 that reacts directly with alkyl halides to
give an acyl product.(107) Scheme 14 illustrates the proposed mechanism.
The insertion corresponds to intramolecular nucleophilic-induced insertion.
Scheme 14
PPh
2
PPh
2
/ \
RX
/ \
(CO)3Fe----Fe(CO)3
(CO)le Fe(CO)3
-\ /-
\ /
PPh
2
PPh
2
31
PPh
2
PPh
2
/ \ / \
(CO)le Fe(CO)3 (CO)le Fe(CO)3
1\ /- 1\ /-
R PPh
2
ROC PPh
2
10.2.2. Alkene, Alkyne, and Carbene Insertion
A LCAO-MO-SCF calculation of equation (45) suggests that the
reaction is best described as olefin insertion and not hydride migrationyo8)
Good 1T-donor ligands are predicted to promote the reaction.
[RhH
2
(CI)(PH
3
h(C
2
H
4
)] 4 [RhH(CO)(PH
3
h(Et)] (45)
Alkyne insertion to give vinylnickel complexes as shown in equation
(46) has been carefully studiedyo9) The reaction occurs rapidly at room
temperature to give a mixture of cis and trans products. The relative
reactivity of different alkynes is Ph
2
C
2
"" PhC
2
H "" Me02CC2C02Me ""
PhC2Me t-BuC2H "" t-BuC2Me Me
2
C
2
"" Et2C2. Reaction (46) is very
266
Me
/
(acac)Ni
'\.
PPh
3
THF /
+ RC
2
R' (acac)Ni
'\.
C(R)=C(R')Me
(46)
PPh
3
regioselective, with unsymmetrical alkynes always placing the larger R
group nearer the metal. The reaction is strongly inhibited by PPh
3
suggesting
that the initial step is alkyne association along with phosphine loss. This
initial step is thought to be rapid and to have an associative mechanism.
The crystal structure of the R=R'=Ph product shows the insertion to be
trans. Furthermore, the trans-complex must be the kinetic product since
isomerization slowly occurs to give a cis/trans mixture. Other alkynes give
a mixture of cis and trans kinetic products. This does not imply trans
addition, however, and a cis-addition mechanism supported by measure-
ments of the cis/trans kinetic product ratio with R' = CH
3
and CD
3
is
suggested (Scheme 15). The insertion step (k
o
) is probably rate determining
and gives the coordinatively unsaturated cis complex 32 that can isomerize
to trans 33 or be trapped by L (PPh
3
). The isomerization 33 32 is not
Scheme IS
/L
lic == CR
RC
2
R'
:..
(acac)Ni/
+ L (acac)Ni +
...
'l1e
'l1e
1,
R l1e
R R'
(acac)Ni >=\R'
.t!
k1[L] )={
...
(acac)Ni l1e
33
k_1[L]
32
1,[1-1
1,[l]
)=(l1e
R R'
>=<
(acac)Ni R'
(acaclNi l1e
\
\
L
L
267
unimolecular because excess PPh
3
does not affect the cis/trans product
ratio. Instead both isomerization and product forming steps are postulated
to involve phosphine. The isomerization pathway may be catalyzed by PPh3
by addition to the olefin to give intermediate 34.
R PPh
3
\ / I
?C-C\-R
(acac}Ni
Me
34
The kinetics of reaction (47) give a two-term rate law, equation
(48).(110) A mechanism is shown in Scheme 16. In THF and CH
3
N0
2
the

+ )
R, /R
C=C ....
/ \
/Mn(CO)4
Me 0
3S
(47)
(48)
k 1 path dominates, suggesting solvent assisted CO insertion (k 1). In benzene
the associative path (k
2
) dominates. The value of k1 was found to be
independent of the nature of the alkyne, but k2 increases as R in R
2
C2
becomes more electron withdrawing. The reaction between
[Mn(CO)s(COMe)] and Me02CC2C02Me to give complex 3S is zero
order in alkyne and involves rate-determining CO dissociation prior to
I
. . (110)
acety mlgratlOn.
Scheme 16
[MElln(CO)5]
k2jr
k-2 r. J
ll1n(CO) ,COMe
J
X
RC=CR
11eC0, I /CO
I1n
OC/ I 'CO
CO
)
...
R
s
'C=C ..........
R
, "-
...
j I1n(CO),
Me/ """0"
Insertion of a zirconoxy carbene into a niobocene hydride bond,
Scheme 17, has been studied. (111) The value of k 1 was obtained by a spin
saturation transfer technique. The a-hydride elimination from 37 is about
4100 times faster than CO trapping at 1 atm CO in benzene, i.e., k-1 :::=
4100kz. Migration of alkyl groups from complex 36 having a Nb-R bond
can be induced by alkynes. The reaction is more complex than that in
Scheme 17 but it is possible to arrive at a kinetic order for migration to
the carbene: H CH
3
> CHzC
6
H
4
0Me > CH
Z
C
6
H
s
. The greater stability
of three-center two-electron bonds involving hydrogen is suggested as an
explanation of this order.
..... H
CPNb = C
Scheme 17
I '0 -
H I
H
36
) - CH
2
-
CO I I
CO H
10.2.3. Insertion of Other Groups
- CH
2
-
I
H
37
A review of transition metal SOz complexes contains a section on SOz
insertion reactions.(1l2) The insertion of SeOz and TeOz into the Mo-R
bond, equation (49), has been accomplished by activation of SeOz and
Te02 in a metal evaporator and condensation in an ether matrix at
_196C.(113.114)
[(C
7
H
7
)Mo(CO)zR] + E0
2
-+ [(C
7
H
7
)Mo(CO)zEO
z
R]
(R = Me or Ph; E = S, Se or Te) (49)
Migratory insertion of NO is not a common reaction, possibly because
there are few examples of alkylnitrosyl complexes. (115) A recent example
o
NO NR
/ THF /
CpCo + PPh3 -------+ CpCo
"- "-
(R = Me or Et) (50)
R PPh
3
is given in equation (50). The rate at lOoC quickly reaches a limit as the
PPh
3
concentration is increased, and the usual R migration mechanism is
postulated. (115)
Insertion of sulfur into a metal-carbene bond is shown in equation
(51).0
16
) The initial step is postulated to be attack of the isothiocyanate
(51)
sulfur on the carbene carbon, and indeed a correlation was found between
the rate constant for reaction (51) and the equilibrium constant for PBU3
addition to the carbene carbon of complex 38.
Chapter 11
Metal-Alkyl Bond
Formation and Fission;
Oxidative Addition and
Reductive Elimination
11.1. Introduction
The eighteen months under review has produced many interesting papers
both on the metal-alkyl bond, and on oxidative addition and reductive
elimination. Space available has forced selection, so that in choosing papers
for comment priority has been given to those which present genuine
evidence for the mechanism of reaction for a particular process or which
measure useful rates especially if activation parameters are also determined.
Relevant work on equilibrium constants, enthalpies of reaction, and bond
dissociation energies has also been included.
Three review articles have appeared which are useful in placing oxida-
tive addition in a wider context. Halpern(1) has written on homogeneous
catalytic hydrogenation pointing out, among other things, that the oxidative
addition step in the manufacture of DOPA is rate limiting at room tem-
perature but not at -40C. Many examples of reactions of H2 and metal
ions are to be found in Brothers' article(2) on heterolytic activation of
hydrogen, while Jardine's review(3) of [RhCl(PPh
3
hJ contains many illustra-
tions of oxidative addition.
271
272
11 Metal-Alkyl Bond Formation and Fission
The first section of this review, 11.2, deals with making and breaking
of the u-metal-carbon bond (in alkyl and aryl systems) both by direct
fusion and fission, and also by transalkylation. Oxidative addition and
reductive elimination follow in the second section, 11.3. Where two metal-
carbon bonds are formed or broken in the same overall process, as occurs
with metallacycloalkanes, the work is included in 11.3.
11.2. Metal-Alkyl Bonds
Because of the amount of work on Cr(III)-C and Co(III)-C bonds
and because it also provides a basis for the understanding of other elements,
these metals are taken first, Sections 11.2.1 and 11.2.2. Cobalt is further
subdivided into Co(III): simple u-Co-C bond fission, Section 11.2.2.1, and
then trans alkylation, Section 11.2.2.2, followed by Co(II) and Co(IV),
Section 11.2.2.3. Thereafter the review more or less runs from left to right
across the Periodic Table, in Section 11.2.3.
11.2.1. Chromium
The cleavage of the Cr-C bond in [(H
2
0)sCr-Rf+ can, in principle,
be heterolytic or homolytic leading to Cr(II) or Cr(III) species, respectively.
The heterolytic process [equation (1)] is reversible, equilibrium lying very
[(H
2
0)sCr-R]2+ [(H
2
0)sCr]2+ + 'R (1)
much to the left, of course. The rapid reaction of oxidizing scavengers with
either or both products enables (1) to be studied. When R is 'CHMe2,
k1(25C) is 1.78 x 10-
4
S-l, while K
1
(25C) is estimated to be about 3 x
10-
12
M.(4) Espenson's group(5) has also estimated rate constants and activa-
tion parameters for (1) when R is various ex -hydroxy- and ex -alkoxy-methyl
groups (see Table 11.1). Increase in bulk considerably accelerates the rate,
although electronic factors are important as well; d. R = CH(Me)OH and
CH(CF
3
)OH. Values of aGi correlate moderately well with the corres-
ponding free energies of activation for the homolytic fission of the R-R
bond. asi are large as expected for an SH1 process.
Scavengers can be used to suppress the homolytic reaction (1) in which
case the heterolytic cleavage process can be observed. (5) In the case of
[(H
2
0)sCrRf+ where R is ex -hydroxy- or alkoxyl-methyl group, both
[H+]-independent and -dependent pathways are observed,(S) which are
suggested to be as in equations (2) and (3). The rate-determining steps in
both (2) and (3) are sensitive to R, the latter being more so (see Table 11.2).
Gold and Wood(6) have remeasured k3 for R = CH
3
at 25.0 C and have
11.2

Metal-Alkyl Bonds 273
Table 11.1. Rate Constants and Activation Parameters for the Homolytic Cr-C
R
CH
2
0H
CH(Me)OH
CH(Et)OH
CMe20H
CMe(Et)OH
CEt20H
CMe(Pri)OH
CMe(Bu')OH
CH
2
0Et
CH(Me)OEt
CMe20Pri
CH(CF
3
)OH
Fission Process in Reaction (1) at 25.0C (Ref. 5)
Mfi asi
ki/s-I
Ikcalmol-
I
leal mol-
I
K-
I
3.7 x 10-
5
30 22
8.5 x,1O-
4
1.0 x 10-
3
32.5 37
1.3 x 10-
1
27.2 28.6
9.2 x 10-
1
25.9 28
8.4 23.2 24
2.2 x 10
1
21.6 20
3 x 10
2
22 27
<10-
6
2 x 10-
3
30.1 30
5.8 24 25
<3 x 10-
5
CrC
2
+ : CrOH
2
+ + HC [
HO'" H]2+
Cr ... C
[
H," OH2]3+
CrC2+ :
Cr C
-----+ Cr
3
+ + HC
Table 11.2. Rate Constants for the Rate Determining
Steps in (2) and (3) at 25.0C
R
CH
2
0H
CH(Me)OH
CH(Et)OH
CMe20H
CMe(Et)OH
CEt20H
CMe(Pri)OH
CH
2
Et
CH(Me)OEt
CH(CF
3
)OH
6.6 X 10-
4
1.9 X 10-
3
3.2 X 10-
3
3.3 X 10-
3
8 X 10-
3
3 X 10-
3
3.5 X 10-
3
<10-
6
,..5 x 10-
7
<10-
6
4.65 X 10-
4
1.2 X 10-
3
2.1 X 10-
3
4.7 X 10-
3
0.47
0.86
0.30
<10-
6
3.8 x 10-
5
<10-
6
aoi
Ikealmol-
I
23.6
21.6
21.5
18.7
17.6
16.2
15.65
14.1
21.1
16.5
(2)
(3)
274 11 Metal-Alkyl Bond Formation and Fission
also obtained activation parameters. The cleavage of the Cr-R bond
in the analogous [(EDTA)Cr-Rf- complexes (where R represents 0'-
hydroxy alkyl groups) also proceeds by heterolytic pathways, one indepen-
dent and the other dependent on [H+]. (7) Rate constants for the former
are very similar to those for [(HzO)sCrR]z+ as in (2) and Table 11.2.
However, those for the latter are some 10
4
-10
6
times larger than their
analogs in (3), suggesting that the proton may be supplied from one of the
carboxylic acid groups of the EDT A.
Cr-C bond fission in [(HzO)5Cr-CH(COOH)CH2C5H4NH]3+ occurs
by a different mechanism,(8) a proton-assisted migration of Cr from C to 0
(giving a carboxylate complex) as in (4). No [H+]-independent path is
Cr-CH(COOH)C + H+ ----+ CrOC(=O)CHzC + H+ (4)
observed. In the case of the bidentate systems derived from succinic acid,
e.g., both the depen-
dent and independent paths are observed.(S) For both, the rate-determining
step is considered to be fission of the Cr-O link because of closeness of
energies of activation to those observed for the aquation of the
[(H
2
0)sCrOOCCH
3
f+ system. After this step, breaking of the Cr-C link
is fast.
The t3 -hydroxyalkyl species, [(H
2
0)sCr-CH
2
CH
2
0Hf+, can be
formed as a transient species in water by various means. It decomposes
by a pathway first order in [H+] (and another that is independent
of acidity but almost imperceptible) with parameters(9): k(25C) =
1.4 x 10-
4
M-
1
s -\ ilit = 15.8 kcal mol-
1
and aS
t
= 13.8 cal mol-
1
K-
1
.
In contrast to reaction (3), which refers to a -hydroxyalkyl systems, the
organic product is ethene and not ethanol. Moreover the rate constant is
large compared with k3 for R = Pr", which is 6.S x 10-
5
M-
1
s-1 at 2S.0C
(although it is not out of line with values in Table 11.2). It is proposed that
a 1T intermediate is produced by t3 -elimination of OH-, giving a pathway
as in equations (5) and (6).
[(H
2
0)sCrCH
z
CH
z
OHf+ + H+ [(H
2
0)sCr(11
2
-C
Z
H
4
)]3+ + H
2
0 (5)
[(H20)sCr(l1z-C2H4)]3+ + H
2
0 --+ [Cr(OH
2
)6]3+ + C
2
H
4
(6)
While many species can react with R produced in (2), it is also possible
for the organo group to be attacked in [(H
2
0)sCrRf+ itself. Bakac and
Espenson (10-13) have made a thorough study of the kinetics of such reactions
in which R is an a -hydroxyl alkyl group. When the attacking species are
or three pathways are observed. (lUI The first is not dependent
on concentration of these ions, but the other two are. The second does not
11.2 Metal-Alkyl Bonds
275
involve [H+], but the third, which is most important, does. For this last
pathway, steps such as (7) and (8) are proposed (although the process may
[CrCH
2
0Hf+ + Cu
2
+ [CrCH
2
0Cu]3+ + H+
[CrCH
2
0Cu]3+ -+ Cr
2
+ + Cu + + H
2
CO
(7)
(8)
be more complicated for Fe
3
+). The second pathway is similar but does
not involve deprotonation as in (7). Reaction (7) is considered to involve
a slow electron transfer process, since change of R from CH
2
0H to
CH(Me)OH has little effect on the rate, while introduction of CH(CF
3
)OH
as R reduces it by 10
3
. V0
2
+ behaves somewhat similarly to Cu
2
+.(l1)
Unlike their organocobalt (N
4
-chelate) analogs, these compounds do not
react with two-electron oxidants, presumably owing to the inaccessibility
of the +1 oxidation state. (10)
For attack by Hg;;, three different types of initial reactions are sug-
gested(12) depending on R, e.g., (9)-(11). Subsequent reaction patterns are
somewhat complicated. Pathway (11) resembles (7) and (8), while (9) is a
conventional SE2 process. [The rate of reaction (12) has also been deter-
mined.f
2
)
[CrCH
2
0H]2+ + Hg2+ -+ Cr
3
+ + HgCH
2
0H+ (9)
[CrC(Me2)OHf+ + Hg2+ -+ Cr2 + Hg + + Me2CO + H+ (10)
[CrCH(Me)OH]2+ + Hg2+ -+ H+ + [CrCH(Me)OHg]3+
-+ CH
3
CHO + Cr
3
+ + Hg(O)
(or Cr
2
+ + Hg +) (11)
+ H
2
0 -+ Hg(O) + HCHO + CH
3
0H + H+ (12)
The three cyanoalkyIchromium(III) species, in which R is CH
2
CN,
CH
2
CH
2
CN, and CH
2
CH(Me)CN, can be formed in solution by reaction
of Cr;; and R. They tend to resemble a -haloalkyl rather than alkyl or
hydroxy alkyl complexes in being resistant to protonolysisY3) The Cr-C
bond is not cleaved by oxidizing agents such as Cu
2
+ and Fe3+. However,
Hg2+ causes trans alkylation as in (13) in a process that is first order in each
reactant and probably SE2.
(13)
11.2.2. R-Co(lII)[N
4
] and R-Co(IlI)[N
2
0
2
] Systems
The chemistry of low-spin organo-cobalt compounds such as the
cobalamins, the cobaloximes, and many Co[N4]- and Co[N20
z
]-containing
conjugated macro cyclic ligands is closely related to that of the organo-
chromium species just discussed. However, in the case of cobalt three
oxidation states are accessible after fission of the Co-C bond, namely, I,
II, and III.
11.2.2.1. Bond Breaking
Halpern's group and Espenson's group have both tackled the mechan-
ism of homolytic fission; is it as simple as equation (14)? The first(14) group,
on the basis of kinetics and product distributions, have shown that
the thermal decomposition of [py(saloph)Co-R] in pyridine proceeds (in
the presence of a radical trap, XH) by two pathways, both of which probably
involve the formation of a geminate radical pair. The first involves reactions
(15)-(17), the second (15), (18), and (19), when R is, for example, C
3
H
7
.
Co-R Co(II) +'R (14)
Co-C
3
H7 {Co(II),C
3
H';} (15)
{Co(II),C
3
H;} Co (II) + C
3
H; (16)
C
3
H; +XH -.
C3
HS+X
(17)
{Co(II),C
3
H;} -.
C3H6 + CoH (18)
CoH -. Co(lI) + !H
2
(19)
The {3 -hydrogen elimination (in the second pathway) probably proceeds
through the geminate pair. When {3 elimination is impossible when R is
neopentyl, for example, decomposition occurs only by the first pathway.
A somewhat similar mechanism emerges from a reinvestigation
of the decomposition of [H
2
0(dmgHhCo-CH(Me)Ph] by Gjerde and
Espenson. (15) Kinetics studies in aqueous methanol suggest that both the
complex itself and its conjugate base are reactive. In both cases a (3-
elimination process gives styrene and hydrogen, as in (20) and (19), and a
homoloytic fission process with radical recombination yields four dimers
of 'CH(Me)Ph, equations (21) and (22). The reversibility of reaction (21)
CoCH(Me)Ph -. PhCH=CH
2
+ CoH (20)
CoCH(Me)Ph Co(II) + 'CH(Me)Ph (21)
'CH(Me)Ph -. dimers (22)
is demonstrated by greater formation of styrene as Co(lI) accumulates.
The {3-elimination pathway does not involve formation of R' even in a
geminate pair.
Equilibrium (21) must also be shifted to the left when the axial ligand
is a pyridine, since then the dimers do not appear to be formed. In that
11.2 Metal-Alkyl Bonds 277
CoCH(Me)Ph Co + PhCH=CH2 + !H2 (23)
case the species in reactions (19)-(21) come to equilibrium, as in (23). Ng,
Rempel, and Halpern(16) have continued their studies on this system (which
differs from that of Gjerde and Espenson above in having a pyridine or
imidazole in place of water as axial ligand). In addition to measuring
Halpern's group estimate the bond dissociation energy for (21), DCo- c (see
Table 11.3). These quantities differ from each other about 2 kcal mol-t,
which is the activation enthalpy for a diffusion-controlled process such as
(-21) or (-14). Thus there is numerical consistency if the rate-determining
step in the forward reaction (23) is identified with (21) [or (14); see later]
so that 6.Hi3 == Mlil and if = 2 kcal mol-t, since -
= which is by definition equal to DCo-
R
approximately.
However, if (21) is rate determining, styrene has to be formed from
CH(Me)Ph as in (24) and not directly as in (20). It is considered probable
Co (II) + 'CH(Me)Ph ---+ CoH + PhCH=CH
2
(24)
that a geminate radical pair is involved as in (15) and (18). Perhaps that
is why the values of (on the assumption of being equal to are
small compared with 6.SL cf. Tables 11.3 and 11.1. The fact that a rise in
the basicity of the pyridine increases the values of (assuming
equivalence to and of D
co
-
R
, which is the opposite of what is often
observed in heterolytic ligand dissociation, points to a change from Co(III)
to Co (II) in (21), suggesting that CoR is somewhat carbanionic.
The assumption that is 2 kcal mol-\ together with the values
of Mli4 for the thermal decomposition of [py(saloph)Co-R] mentioned
in the last paragraph but two, enable DCo- R to be obtained for this system
as wellY4) The effect of the bulkiness of R can be seen in Table 11.4. In
this table parameters are included for (25) (R-
H
= alkene). [Although
Co-R ---+ Co (II) + R-
H
(25)
Table 11.3. Parameters (Ref. 16) for the Reaction
{py(dmgH}2Co-CH(Me)Phj {py(dmgH}2Coj + PhCH=CH2 + 1H2
py
4-Aminopyridine
4-Methylpyridine
Pyridine
4-Cyanopyridine
Imidazole
DCa- R,
Ical mol-
1
21.2
20.1
19.5
17.9
20.8
4.0
6.0
7.3
13.1
1.7
ill" ,
kcal mol-
1
23.1
21.8
21.6
20.1
23.0
3.8
0.9
-0.2
-3.9
1.9
R

C
H
2
C
H
2
C
H
3

C
H
(
C
H
3
h

C
H
,
C
(
C
H
3
h

C
H
2
C
6
H
5

T
a
b
l
e

1
1
.
4
.

P
a
r
a
m
e
t
e
r
s

f
o
r

R
e
a
c
t
i
o
n
s

(
2
5
)

a
n
d

(
1
4
)

f
o
r

{
p
y
(
s
a
l
o
p
h
)
C
o
-
R
J

(
R
e
f

1
4
)

k
2
S

(
7
0
C
)

/
s

1
.
0

X

1
0
-
5

1
.
9

X

1
0
-
3

t
i
l
l
i
s
,

k
c
a
l

m
o
l
-
I

2
3
.
4

1
9
.
8

k
1
4

(
7
0
C
)

c
a
l

m
o
l
-
I

K
-
1

/
S
-
1

-
1
5
.
1

4
.
7

x

1
0
-
4

-
1
5
.
5

5
.
7

x

1
0
-
2

3
.
4

x

1
0
-
2

1
.
2

x

1
0
-
2

k
c
a
l

m
o
l
-
1

c
a
l

m
o
l
-
I

K
-
1

2
7
.
1

2
.
6

2
1
.
8

-
2
.
9

2
0
.
3

-
6
.
2

2
3
.
6

1
.
3

D
c
o
-
R
,

k
c
a
l

m
o
l
-
I

2
5

2
0

1
8

2
2

.
.
.
.
.
.
.

.
.
.
.
.
.
.

l
:
i

:
i
:

;
;
;
:
:

'
:
:
.
.

t
J
:
:
l

C
)

3

s
:
:
.

5
'

s
:
:
.

s
:
:
.
.
.
.

0
'

this reaction is similar to (23), is not identified with MlI4 as
was.]
The decomposition of alkylcobalamin by (3 -elimination of H, whether
by a route analogous to (18) or (20), is impossible in neopentyl and benzyl
cobalamins and cobinamides. Schrauzer's group(17,lS) has studied the
decomposition, in the absence and presence of O
2
, of such compounds.
The slowness of the reaction under the first conditions points to reactions
(14) and (26), equilibrium lying to the left in the former and the latter
R + O
2
+ Co(II) ..... R0
2
Co ..... products (26)
being fast. Activation parameters are given in Table 11.5. The faster rates
of decomposition of the cobalamins compared with the cobinamides are
attributed to distortion of the corrin ring in the former caused by coordina-
tion of the dimethylbenzimidazole group. Both decompose more slowly
than the [py(saloph)CoR] compounds in Table 11.4. Decomposition is some
six to eight times faster when R is, say, CH
2
C(Me)(COOEth rather than
CH
2
CH(COOEthYS) Data are also given in Table 11.5 for isopropyl- and
isobutyl-cobalamins; (3 -elimination giving alkene accounts for the decompo-
sition of 100% of the former and 28% of the latter, but the activation
parameters are similar to those where the reaction is homolyticY7l
Brown's group have continued their work on the base-catalyzed
decomposition of alky1cobaloximes. Studies(19) using deuterated materials
show that the ethane produced from [H
2
0(dmgHhCo-Et] in basic condi-
tions, equation (27), is formed as the result of homolytic Co-Et bond fission
as in (14), Ef then abstracting H either from a methyl group on the dmgH
ligand system or from the solvent (water or methanol). On the other
hand,(19) cleavage of the Co-C bond in the methyl analog is heterolytic
giving Co (III) and a carbanion (which by reaction with H+ gives methane).
Table 11.5. Activation Parameters for the Decomposition of Various
Cobalamins and Cobinamides in Air (at pH 7), cf. Equation (14); for
R = Pr
i
and Bu i, {3-Elimination Also Occurs
k
Mit
IlSt
Is-I
Ikeal mol-I leal mol-I K-
1
Neopentylcobalamin
1.5 x 10-
4
23.4 2.6
Neopentyleobinamide
3.9 x 10-
5
32.1 17.3
8enzyleobalamin
1.9 x 10-
4
24.6 12.3
8enzylcobinamide
3.6 x 10-
5
26.9 9.2
Isopropylcobalamin
3.3 x 10-
4
20.7 -0.3
Isobutylcobalamin
1.1 x 10-
4
26.8 3.8
280
Table 11.6. Rates of Reactions (27) and (28)
at 50.o
o
e (Ref. 20)
lO6k
27
lO6
k28
L
/M-
1
5-
1
/M-
1
5-
1
OW 6.1 1.1
py 3.2 5.3
MeSEt 1.1 0.51
CW 8.8 2.6
Perhaps the failure to detect a homolytic pathway is due to the high rate
of the back reaction (-14) when R is Me.
Ethene also can be produced in the base-catalyzed decomposition of
[H
2
0(dmgHhCoEt], equations (27) and (28).(20) Rate constants are of the
[CH
3
CH
2
Co(dmghL] + OH- --. C
2
H
6
+ Co(III) (27)
[CH
3
CH
2
Co(dmghL] + OH- --. C
2
H
4
+ Co (I) (28)
same order of magnitudes (see Table 11.6), and contrast with the decom-
position of [CH
3
Co(dmghL] to methane for which the corresponding
parameters are all immeasurably small except for L = OH-.
As with the [(H20)5CrR]2+ systems, [H
2
0(dmgHhCoR] seems to
decompose by a different mechanism when R is a (3 -hydroxy or alkoxyalkyl
group, viz. CH
2
CH
2
0H, CH
2
CH
2
0Et, or CH
2
CH
2
0Ph.(21) In the last two
cases two steps can be detected in the overall decomposition of
[H
2
0(dmgHhCoCH
2
CH
2
0R'] which yields ethene, R'OH, and
[Co(dmgHh(OH
2
h]. The fact that some [H
2
0(dmgHhCoCH
2
CH
2
0H] can
be formed when R' is Et or Ph together with an equality in the rate constants
for the second step for these two R' indicate a common intermediate as in
(29) and (30). Reaction (29) is reversible when R is H, while the intermedi-
ate may be 1T' bonded as shown; cf. reactions (5) and (6).
[H
2
0(dmgHhCoCH
2
CH
2
0R'] + H+ --.
[H20(dmgHhCo(1j2-CH2CH2)] + R'OH (29)
[HzO(dmgHhCo( 1j2-CH
2
CH
z
)] -+ C
Z
H
4
+ [Co(dmgH)z(OH
2
)2] (30)
This sort of intermediate is postulated in another system: cyanide ion
causes cleavage of the Co-CH
2
C(O)OCH
3
bond in [(methoxycar-
bonyl)methyl]cobalamin, resulting in the formation of methyl acetate. (22)
Analysis of kinetic isotope effects and other rate data indicate that an
intermediate is formed, which is suggested to be the 1T'-bonded enolate,
[NCCO{1j2 -(;H
2
=(;H(O-)Me}].
11.2 Metal-Alkyl Bonds
281
The radicals produced in (14), the Cr-R bond fission reaction, can be
trapped by [HzO(dmgHhCo-R'] systems as in equation (31). Rate constants
[HzO(dmgHhCo-R'] + 'R --. R'-R + [Co(dmgHhOH
z
] (31)
have been obtained for the second step,(Z3) viz. R' = CHzPh; R =
CH(Me)OCH
3
: 5.9 x 10
6
M-
1
s-r, R = C(Mez)OH: 5.2 x 10
6
M-
1
S-1 at
25.0 C in water. Slightly higher values are found for the protonated form
of [R'-Co(dmg)zOH
z
].
11.2.2.2. Transalkylation
Transmethylation between methylcobalamin and tin (II) chloride in
aqueous hydrochloric acid gives methyltin(IV) and aquocobalamin (HzO-
BIz) and B
I2r
under anaerobic and aerobic conditions. (Z4) Studies of kinetics
and stoichiometry and the effect of added aquocobalamin suggest reaction
(32) followed by either (33) or (34) and (35), respectively in the
Me-B
12
+ Sn(I1)

B
12r
+ MeSn(III), (32)
...-
MeSn(III), +

B12r + MeSn(IV) + H2O (33)
...-
MeSn(III), + Oz

MeSn(IV) + ... (34)
...-
B1Zr + HzO + 02

+ ... (35)
...-
absence or presence of 02. Rate constants, which refer to (32), for methyl-,
and the corresponding reactions of ethyl- and chloromethyl-cobalamin are
at 23C: 1.04, 1.66 x lO-
z
, and 7 x 10-
3
M-
1
S -1. Equation (32) is assumed
to be an SH2 process.
Thayer(ZS) has measured rate constants for the demethylation of
methylcobalamin by complex halides such as [AuCI4r. [TlBr4r. and
[PtCI
6
f-. Fanchiang(26) has shown that methylcobalamin reacts with
[AuX
4
r (X = CI or Br) with a 2: 1 stoichiometry to give aquocobalamin,
an oxidized corrin ring, and colloidal gold. (Z6) Kinetic data have been
analyzed in terms of a pre equilibrium (36), electron transfer (37), and then
reactions (38)-(40).
Me-B
12
+ AuX'; {[Me-Bn],[AuX
4
r} (36)
{[Me-B
12
],[Au(III)X
4
r} --. {[Me-B
12
t,[Au(II)X
4
]2-} (37)
{[Me-B
12
t,[Au(II)x
4
f-} --. + Au(II) + Me' (38)
Me' + [AuX
4
r --. MeX + Au (II) (39)
2Au(II) + corrin --. 2Au(0) + oxidized corrin (40)
Corresponding to the monoalky1cobalt(III) complexes are various
dialky1cobalt(III) systems. Transmethylation can occur from various such
trans-dimethyICo[N
4
] complexes to Zn
2
+, Cd
2
+, and Pb
2
+ (or M
2
+). Spec-
trophotometric titrations and 1H nmr in acetonitrile suggest reactions (41)
and (42). Me3Pb + and Me2Pb2+ behave similarly giving Me4Pb (going
through Me3Pb+ in the second case).(27)
[Me
2
Co[N
4
]] + M2+ + CH
3
CN -+ [MeCo[N
4
](CH
3
CN)] + MeM+ (41)
[Me2Co[N4]] + MeM+ + CH
3
CN -+ [MeCo[N
4
](CH
3
CN)] + Me2M (42)
11.2.2.3. Co(JJ)-C and Co(IV)-C Bonds
Two examples have been described of the formation of transient
dimethy1cobalt(IV) macrocyclic complexes, Me
2
Co(IV)[N4], by elec-
trochemical oxidation of the corresponding cobalt(III) compound. These
decompose to a monomethy1cobalt(III) species and ethane; deuterium
labeling and radical-trapping experiments show that the process involves
homolytic Co-C bond fission as in (43). There is thus a formal similarity
to reaction (14). (28)
(43)
Reduced alky1cobaloxines have been produced by matrix methods
at 77 K.(29) On warming [py(dmgHhCoCH
2
Phr gives PhCH
2
and [Co(II)(dmgHhpy], but the methyl analog yields CH
l
and
[Co(I)(dmgHhpyr. Thus there is some similarity to the base-catalyzed
cleavage of [H
2
0(dmgHhCoR] which gives a carbanion with R = Et and
a radical when it is Me.
Fission of the ethyl-cobalt bond in the tetraphenylporphyrin
[EtCo(IV)(TPP)] involves transalkylation from cobalt to nitrogen to give
a cobalt(II) N -ethyl-TPP complex. (30) The same also occurs in reduced
alkylcobaloximes. (31)
Armentrout and Beauchamp(32) have used ion beams to study the
reaction of the positive ion, Co +, and various alkanes. A typical reaction
is that with n-propane, which yields and CoC
2
H; (as
well as CH
l
, C
2
H;, and CH
4
). Possible intermediates include H
3
C-Co + -
C2HS after which H3C(H)Co+(112-C2H4) may be formed. DO(CO+-CH3)
and DO(Co-CH3) are found to be 61 and 41 kcal mort, respectively, the
latter agreeing reasonably with data for Mn, Re, and Pt-CH3 bonds.
Cyclobutane and cyclopentane may form [cobaltacycloalkanet ions.(33)
Transalkylation(34) takes place between [Cp2ZrMe2] and THF to
give ultimately [Cp2Zr(BH4h] and methylboron species. It is postulated
that the process involves insertion of BH3 into a Zr-Me bond and intermedi-
ates such as [Cp2Zr(BH3Me)Me] and [Cp2Zr(BH2Me2)H].
Replacement(3S) of the PhCH
2
group in various Zr and Hf compounds
by Bu;NO' involves an SH2 process as in (44). Rate constants vary by
+ [Cp2Zr(CH2Phh] --+
[Cp2Zr(CH2Ph)(ONBum + PhCH; (44)
several orders of magnitud,e for different compounds. New metal-methyl
bonds as in (45) and (46) can be formed by irradiation of [Cp2Ti(CH3h],
which produces radicals. (36)
1/2[Mn2(COho] --+ [Mn(CO)SJ 'CH
3
[CH
3
Mn(CO)s] (45)
[ReBr(CO)s] + 'CH
3
--+ [CH
3
Re(CO)s] + Br' (46)
Iron(II) and iron (III) deuteroporphyrins react with methyl radicals(37)
with rate constants of 3.9 x 10
9
and 2.9 x 10
9
M-
1
s-I, respectively, giving
Fe(III)-CH
3
- and Fe(IV)-CH
3
-containing species. The latter undergoes a
methyl transfer reaction with iron(II) deuteroporphyrin to give the Fe (III)-
CH
3
compound with a second-order rate constant of 4 x 10
8
M-
1
S-1. An
alkyl-iron(III) species is produced(38) in reaction (47).
4-0
2
NC
6
H
4
CH; + [Fe(II)(TPP)] --+
[4-0
2
NC
6
H
4
CH
2
-Fe(III)(TPP)] (47)
Alkyliron porphyrin complexes can also be formed by the attack on
alkyl halides by Fe(I) systems, made by electroreduction as in, e.g., (48).
[Fe(I)(porph)] + BunX --+ [Bun-Fe(II)(porph)] + X- (48)
Rate constants fall, r > Br - > Cl-, viz. (porph = OEP) 300, 170,
0.3 M-
1
s -1, and are slightly smaller than for the corresponding reaction
involving cobalt [e.g., Fe(TPP), X = Br, 4; Co(TPP), X = Br, 30 M-
1
S-1].
Reaction (48) is considered to be SN2, like that of the cobalt analogs. The
alkyliron(II) compounds can be electrooxidized to alkyliron(III) and alkyl-
iron(IV) species, the last being rather less stable with life times of the order
of a millisecond. (39)
The cleavage of the Fe-C link by copper(II) chloride and bromide in
[(71
s
-CsHs)(OChFe-R] has been studied in CH
2
Ch. In general a one-
electron transfer yields [Fe-Rt[CuX
2
r. When R is Me or PhCH
2
the ion
pair breaks down within the solvent cage by SN2 attack of the halide on
the a carbon of R (leading to inversion) as in (49). If R is Bun or
[Fe-Rt[CuX
2
r ---+ {FeR .. XCuX} ---+ Fe' + RX + CuX (49)
Me
3
CCH
2
CH
2
, [Fe-Rt escapes and undergoes homolysis [equation (50)],
(The radicals Fe' and R abstract halogen from solvent.) Which mechanism
is preferred seems to depend on the tendency of R to react by an SN2
pathway. [FeCH
2
CH
2
Pht gives a phenonium ion as in equation (51).(40)
[Fe-Rt ---+ Fe+ + R (50)
(51)
Radicals formed using radio frequency glow discharges react with
metal atoms in the gas phase and the resulting species can be trapped by
phosphines at low temperatures, e.g., equation (52).(411
Ni + 2CF3 ---+ [Ni(CF3hJ ---+ [Ni(CF3h(PMe3hJ (52)
Initiation by light, retardation by radical scavengers, and the cyclization
of intermediates indicate that the reaction of primary and secondary alkyl-
mercury halides with the salts of secondary nitro alkanes [equation (53)]
RHgX + ---+ + Hg(O) + X- (53)
takes place by a radical chain mechanism, a modified S RN 1 process. (42)
Reaction (54) is the initiating step, with reactions (55) to (57) maintaining
the chain. Aryl- and 1-alkenylmercury halides either do not react with
nitronates or give bisorganomercury compounds and mercury metal.
RHgX + RHg' + X- + R;CN0
2
' (54)
RHg' ---+ R + Hg(O) (55)
R + ---+ (56)
RR;CNO; + RHgX ---+ RR;CN0
2
+ RHg' + X- (57)
Studies(43) of the relative rates of reaction (58) involving cleavage of
the phenyl-tin bond indicate that by far the most reactive system is that
in which m = 1 and n = 3.
12 + Ph3Sn(CH2)nS(O)mC6H4Me-p ---+
PhI + Ph2(I)Sn(CH2)nS(O)mC6H4Me-p (58)
11.3. Oxidative Addition and Reductive Elimination
The interest in individual steps, particularly in the formation of the
radical anion type of species which were featured in Volume I, e.g., Ni(O) +
11.3 Oxidative Addition and Reductive Elimination
285
RX [Ni(I), is superseded by more examples of the four types of
processes: concerted, radical, radical-chain, and two-step ionic. Under the
mantle of reductive elimination, perhaps not quite correctly, (3 elimination
of hydrogen is included since this process seems able to take place under
very similar conditions to those under which a concerted reaction occurs.
It is interesting to see the use of Hoffmann-type calculations in rationalizing
elimination reaction pathways. Mention should be made also of the
mechanism of processes involving two metal centers.
11.3.1. Pretransition Metals
Whitesides' group(44l provided a significant contribution on Grignard
reagents and has continued its study on the mechanism of formation of
these compounds. The rate of reaction of cyclopentyl bromide with mag-
nesium in rotating disc experiments is mass-transfer controlled.
Molle and Bauer(45
l
have demonstrated that contrary to generally
accepted opinion, the Barbier synthesis does not necessarily involve the
formation in situ of a Grignard-type, organometallic compound.
It would be interesting to know more of the structures of various
species formed when single charged metal ions such as Mg + and Mn + react
with alkyl halides,(46) which are formulated as, for example, Mg(C
3
H
7
Clt,
Mn(C3H6t. Klabunde's group(47l have looked at the question of whether
CH3Br can add oxidatively to metal atoms at the low temperatures of
matrix formation (12 and 77 K). Mg AI, Ga, and In do give CH
3
MBr, but
TI, Ge, Sn, and Pb do not react. Fe, Co, Ni, and Pd do not give CH
3
MBr,
though a CH3Br-M complex appears to be formed.
Et
2
AICH
2
AlEt has been used as a probe to investigate the mechanism
of the reaction of R3AI with a ketone in a 2: 1 (as opposed to a 1: 1)
ratio. (48) Evidence is obtained for the cyclic transition state containing a
bridging R group, as in
" i i
C=O .. AI(R
2
) ... R-AI(R2) ... R
/ '
which links the two aluminum atoms.
11.3.2. Earlier Transition Metals
n-, s-, and t- butyl chlorides react with [Cp2Zr(PPh2Meh] or [CP2ZrL2]
to give the oxidative addition product, [Cp2Zr(Bu)CI], and/or [Cp2ZrClz].
Observation of esr spectra assignable to species such as
[Cp2Zr(III)CI(PPh2Me)] and [Cp2Zr(I1I)Bu(PPh2Me)] led Williams and
286
Schwartz(49) to propose a radical-chain mechanism (62) accompanied by
initiation processes (59)-(61).
[Cp2ZrL2] [Cp2ZrL] + L (59)
[Cp2ZrL] + RCI -+ [Cp2Zr(L)CI] + R (60)
[Cp2Zr(L)CI] + RX -+ [Cp2ZrClz] + L + R (61)
[Cp2ZrL] + R -+ [Cp2Zr(R)L] }
(62)
[Cp2Zr(R)L] + RCI -+ [Cp2Zr(R)CI] + L + R
An interesting slant on whether a reaction can appear to be an oxidative
addition without being so in a formal sense is provided by some zirconium
complexes. The rate of reaction of these species with H2 to give
[Cp3Zr(H)CI] or [Cp2ZrH2] and an alkane follows a sequence:
[Cp2Zr(R)H] > [Cp2Zr(R)CI] - [Cp2ZrR2] > [Cp2Zr(COR)CI]. Formally,
the Zr has an oxidation state of IV and a dO configuration so that oxidative
addition cannot occur. The authors(SO) describe the process as a heterolytic
activation, but suggest that the H2 may overlap with an empty (as opposed
to a full) d orbital giving some formal similarity with oxidative addition.
The oxidative addition of BunBr, Bun I, PhCH
2
CI, and PhCH
2
Br to
the [CpMo(COhr ion is first order in each reagent, and reaction rates are
somewhat susceptible to counterions, additives, and solvent.(S1)
Studying binuclear reductive elimination between [p-X-
C
6
H
4
CH
2
Mn(COMcis-L)] and [HMn(COMcis-L)], L = CO or (p-
MeOC
6
H
4
hP, Halpern's group(S2) have shown that modest changes in
ligands, solvent, or concentration of free CO can result in complete changes
in mechanism from one pathway to another. They propose four distinct
pathways, the essential features of which are given by equations (63) and
(64), (65) and (66), (67) and (68), and (69) and (70), respectively. Only
the third pathway [(67) and (68)] is clearly radical. The first two [(63) and
(64)], and [(65) and (66)] involve bimolecular addition processes preceded
by reorganization of ligands. The formation of the two radicals as an
intermediate step in (70) is proposed to avoid the problem of [HMn(CO)s]
having to react with a saturated species.
[RMn(CO)s] [RMn(CO)4] + CO (63)
[RMn(CO)4] + [HMn(CO)s] -+ RH + [Mn2(CO)9] (64)
[RMn(CO)s] + S [RCOMn(CO)4S] (65)
[RCOMn(CO)4S] + [HMn(CO)s] -+ RCHO + [Mn2(CO)9S] (66)
[RMn(COMphos)] R + [Mn(COMphos))' (67)
11.3 Oxidative Addition and Reductive Elimination
R + [HMn(COMphos)] --+ RH + [Mn(COMphos)J
[RMn(COMphos)] + CO --+ [RCOMn(CO)4(phos)]
[RCoMn(CO)4(phos)] --+ [Mn(CO)4(phos)J + RCO
[HMn(COisl. RCHO
287
(68)
(69)
(70)
Contrasting mechanisms for reductive elimination in a monometallic
system are provided by Kochi's group.(53) Elimination from cis-
[R
2
Fe(bipyh], cis-[R
2
Fe(bipyht, and cis-[R
2
Fe(bipy}z]2+ in THF, for
example, depends on the oxidation state of the iron. For the first group of
compounds retardation of the reaction by free bipy and the formation of
alkane and alkene (R-
H
), but not of R
2
, suggest partial dissociation of
coordinated bipy, (3 elimination, and then hydrogen transfer as in equations
(71)-(73). However decomposition of cis-[R
2
Fe(bipy)zt is not retarded
[R2Fe(1J2-bipy)z] [R2Fe(1J2-bipY)(1J1-bipy)] (71)
[R2Fe( 1J2-bipy)( 1J1-bipy)] + bipy ;:!: [R2Fe( 1J2-bipy)( 1J1-bipyh] (72)
[R
2
Fe(1J2-bipY)(1J1-bipy)] --+ --+ RH + [Fe(bipy)z]x
by free bipy. Radicals, such as Et", can be trapped and products include
R
2
, all of which indicates a mechanism such as (74) and (75). The last ion
appears to eliminate by a concerted process since RH and R-
H
are not
formed, only R
2
, viz. reaction (76).
[R2Fe(1J2-bipy)zt --+ {R,[(1J2-bipy)zRFet} (74)
{R",[(1J2-bipy)zRFet} --+ --+ RH + R-
H
+ RR + [Fe(bipyht (75)
[R2Fe(1J2-bipyhf+ --+ R2 + [Fe(1J2-bipy)z]2+ (76)
In general, iron carbonyls react with organic halides by two path-
ways.(54) However [Fe(COh(AsPh
3
h] and CCl
4
follow only one route,
which is believed to involve radicals since there is an induction period, no
reaction in the dark, and a decrease in rate in the presence of duroquinone.
On the other hand, [Fe(COh(PMe3h] and Mel react only by the alternative
pathway, which has no characteristics of a radical process. This reaction is
first order in each reactant, t::.st being -33 cal deg -1 mol-
1
. A concerted
nucleophilic displacement (two-center SN2) is proposed as in (77), in which
the first step is rate determining.
[Fe(COh(PMe3h] + Mel --+ [Fe(COh(PMe3)z(Metr]
--+ [Fe(CO)z(PMe3h(COMe)I] (77)
The complexes, [(OC)4Fe(R)SiMe3], R = Me or CH
2
Ph, have been
prepared(SS) and are of particular interest to the catalytic olefin hydrosilyla-
tion process, since they undergo a reaction postulated but not previously
observed directly, namely, alkylsilane elimination as in (78).
[(OC)4Fe(R)SiMe3] -. RSiMe3 + [Fe(CO)4] (78)
The scope of the d
6
-. dB change has been extended by formation of
ruthenium(IV) and osmium(IV) species by oxidative addition to metal(II)
compounds as in equations (79a) and (79b).(S6)
[RuCI(PPh
3
hCp] + HPF
6
-. [RuH(Cl)(PPh
3
hCpt (79a)
[OsBr(PMe3hCp] + [NO][PF
6
] -. [Os(NO)(PMe3hCpf+ (79b)
11.3.3. Cobalt, Rhodium, and Iridium
The hydrogenolysis of [CpCo(PPh3)Me2] to give methane has an induc-
tion period, which suggests that simple oxidative addition of H2 is not
involved(S7); moreover, no evidence is found for a radical-chain process.
Instead reactions (80)-(83) are proposed [of which (82) is an oxidative
addition]. Identification of [(Me
s
C
s
)Co(PPh
3
)H
2
] provides evidence
for reaction (82), while kinetically the decomposition of
[(MesCs)Co(PPh3)Me2] in the presence of this hydride can be accounted
for satisfactorily in terms of reactions (80) and (83).
[CpCo(PPh3)Me2] [CpCoMe2] + PPh
3
(80)
[CpCo(PPh
3
h] [CpCo(PPh
3
)] + PPh
3
(81)
[CpCo(PPh
3
)] + H2 [CpCo(PPh
3
)H
2
] (82)
[CpCo(PPh
3
)H
2
] + [CpCoMe2] + PPh
3
-. 2[CH
4
+ 2CpCo(PPh
3
h]
(83)
The chemistry of the [Co(CN)S]3- is by no means always restricted to
the monomeric unit. H2/D2 studies indicate that the addition of H2 to this
species is heterolytic involving a dicobalt species containing not a Co-Co
bond but a CoNCCo unit; reactions (84)-(88) are suggested.(SB)
2[Co(CN)s]3- [(NC)sCo(III)NCCo(I)(CN)4]6- (84)
[(NC)sCo(III)NCCo(I) (CN)4t- +H2
[(NC)sCo(I)NCCo(III)(CN)4Hf- +H+ (85)
[(NC)
s
Co(I)NCCo(III)(CN)4Hf- +H+
[(HNC)(NC)
4
Co(I)NCCo(III)(CN)4Ht- (86)
11.3 Oxidative Addition and Reductive Elimination 289
[(HNC) (NC)
4
Co(I)NCCo(III) (CN)4H]6-
[(HNC)(NC)4Co(I)f- + [Co(III)(CN)sH]3- (87)
[(HNC)(NC)4Co(I)]3- [Co(III)(CN)sH]3- (88)
Enthalpies for the oxidative addition of tetrachloro-1,2-benzoquinone
to [M(dppeh]BF4' where M is Co, Rh, or Ir, have been found to be -196,
-144, and -179 kJ mol-t, respectively, in CH
2
CICH
2
CI at 25C.(S9)
The oxidative addition of methyliodide to trans-[RhCl(CO)(PR
3
h]
is more complicated than previously supposed.(60) When R is Bun, n -C
8
H17'
or n -C
18
H
37
, the product is the expected Rh(III) complex, as in equation
(89); rate constants are approximately equal. However when R is triaryl,
the expected oxidative addition still occurs, but it is complicated by insertion
[RhCI(CO)(PR
3
h] + CH3I ---. [RhCI(I)(CH
3
)(CO)(PR
3
h] (89)
[RhCI(CO)(PR
3
h] + CH3I ---. [RhCI(I)(COCH
3
)(PR
3
h] (90)
as in the overall process [equation (90)], in which [RhCI(I)(CO)(PR
3
)]-
is postulated as an intermediate. An induction period is observed which is
ascribed to the formation of R
3
PMe +. k 89 decreases for R:
corresponding to a fall in the basicity in PR
3
accompanied by some steric
effects. are very different for the Ph and p-Bu
n
C
6
H4 systems, namely,
62 23 and -122 37 J K-
1
mol-
1
.
A novel form of the oxidative addition/reduction elimination process
has been observed which involves transfer of two chloro groups from one
metal center to another, namely, Rh or Ir to Rh, Ir or Pt, as in equation
(91) (L = PMe2Ph or PEt2Ph) in which a double-bridged intermediate is
postulated. (61)
[Rh(III)Ch(CO)L
2
J + trans-[Ir(I)Cl(CO)L
2
J
---. [L
2
(OC)CIRh(1L -ClhICI(CO)L
2
J
---. trans-[RhCI(CO)L
2
] + [IrCh(CO)L
2
J (91)
The first step in the thermal decomposition of the metallocycloalkane
complexes [CpM(CH
2
)n (PPh
3
)] (M = Rh or Ir; n = 4, 5, 6) is decomposi-
tion of the alkane ring with the formation chiefly of alkenes. (62) Activation
energies are about 35 and 70 kcal mol-
1
for the rhodium and iridium
compounds, respectively.
Reductive elimination from rhodium complexes containing u-bonded
unsaturated acyl groups, e.g., [RhCH=CHR(CO)(PPh
3
hClz], gives not
the expected RCH=CHCI but The observed rate law
is first order in [Rh(III)] and [PPh
3
], but also contains inverse terms in
[Cn and [PPh
3
], which suggests a mechanism consisting of reactions (92)
and (93). (63) The intermediate could be
or the metallocyclopropane, [RhCH(PhH H(PPh
3
)}(CO)(PPh
3
)zCI].
[Rh(CH=CHR)(CO)(PPh
3
hClz]
[Rh(CH=CHR)(CO)(PPh
3
hcIt + Cl- (92)
[Rh(CH=CHR)(CO)(PPh
3
hcIt + PPh
3
intermediates
[RhCl(CO)(PPh
3
h] + PhCH=CHPPh
3
(93)
Some useful experiments on oxidative addition to Ir(I) have been
carried out by Louw's group. The first illustrates two types of mechanism.
Addition of methyliodide to [Ir(cod)(phen)tCl- is catalyzed by iodide
ions. (64) The kinetics are compatible with two parallel pathways. The first
(94) involves a concerted process, and the second, (95) and (96), a two-step
Ir(I) + CH3I Ir(III)(CH
3
)I
Ir(I) + r Irr
Irr + CH3I Ir(III)(CH
3
)I + r
(94)
(95)
(96)
ionic mechanism. Presumably reaction (96) is SN2. Kinetic and thermo-
dynamic parameters in methanol are: k
94
(25C) == 9.2 x 10-
5
M-
1
s-t,
== 51.9 kJ mol-t, == -146 J mol-
1
K-t, K95 (25C) == 227 M-t,
k
96
(25C) == 6.4 x 10-
4
M-
1
s-\ == 44.7 kJ mol-I, ==
-159 kJ mol-
1
Thus, in molar iodide the second pathway is some thousand
times faster, a fact which is relevant to the Monsanto acetic acid process
for which this anion is also a catalyst. The large negative values for AS*
suggest a high degree of association in the transition states in both (94)
and (96). Rather similar behavior is observed(65) in the reaction of O
2
with
[Ir(cod)(phen)t in the presence of r, SCN-, C.-, and PPh
3
, or X, in
methanol. For the first two ligands, two pathways are again observed, viz.
(97) and (98) with (99). k
97
(25C) == 1.6 x 10-
2
M-
1
S-1, ==
26.8 kJ mol-I, == -192 J mol-
1
K-
1
For X == rand SCN-, respec-
tively, k
99
(25C) == 0.31 and 0.53 M-
1
s -1, == 40.6 and 43.9 kJ mol-
1
and == -121 and -105 J mol-
1
K-
1
Reaction (99) is slow when X is
CI- or PPh
3
. The associative nature of (97) and (99) is again illustrated by
large negative values of AS* and also of volumes of activation,
Ir + O
2
Ir02
Ir+ X IrX
IrX + O
2
Ir02 + X
(97)
(98)
(99)
-28 cm
3
mol-
1
for (97) and an overall value of -42 cm
3
mol-
1
when [r] ==
0.5 M for (99).
The second set of experiments by Louw's group(66) illustrates the
relative importance of 18-, 16- and 14-electron species in oxidation addi-
tion. Kinetic studies on the reaction of H2 and PhC-CH, or Y, to
[IrH(CO)(PPh
3
h] in benzene at 25C provide evidence for tris, bis, and
monophosphine complexes, all of which can be involved in the overall
reaction scheme [equations (100)-(105)]. Galvinoxyl does not affect rates
[IrH(CO)(PPh
3
h] [IrH(CO)(PPh
3
h] + PPh
3
(100)
[IrH(CO)(PPh
3
h]
.......
[IrH(CO)(PPh
3
)] + PPh
3
(101)

[IrH(CO)(PPh
3
h] + Y
.......
[IrH(CO)(PPh
3
h Y] + PPh
3
(102)

[IrH(CO)(PPh
3
h] + Y
.......
[IrH(CO)(PPh
3
h Y] (103)

[IrH(CO)(PPh
3
)] + Y
.......
[IrH( CO )(PPh
3
) Y] (104)

[IrH(CO)(PPh
3
h Y]
.......
[IrH(CO)(PPh
3
)Y] + PPh
3
(105)

so radicals are probably not involved. For Y == H
2
, (102), (104), and (-103)
are all important, though k103 - 0, while for Y == PhC_CH (103) is
significant, but (104) is more so, with k102' k-102' k-103, and k-104 all being
approximately zero. Thus the 14-electron species is important in both
processes, the 16- for PhC_CH, and the 18- only for H
2
. The last fact
provides evidence for direct attack of H2 on a coordinately saturated species.
The third piece of work(67) uses X-ray photoelectron spectroscopy to
estimate the oxidation number of the iridium ion in the products of reactions
involving iridium(I) compounds as in equations (106) and (107). The
Ir + XY -+ IrXY (106)
Ir + L -+ IrL (107)
oxidation number (of 3.00) when XY is Clz or HCI shows that the process
should be looked upon as oxidative addition, while for L == SCN-, r, PPh
3
,
C
2
H
2
, and C
2
H
4
the addition is nonoxidative, with oxidation numbers
between 0.26 and 1.11. O
2
seems to occupy an intermediate position.
Pearson and Kresge(68) have compared equilibrium constants for addi-
tion of H+ and for oxidative addition of HCI to trans-[IrX(CO)(PPh
3
h]
(X == CI or Br, S == solvent == CH
3
0H); see (108) and (109), respectively.
Ir(I) + H+ + S trans-Ir(III)H(S) (108)
Ir(I) + HCI trans-Ir(III)H(Cl) (109)
Equilibrium constants are close in value to each other pointing to an
equilibrium constant near to 1 for (110). Kinetic expressions for the rate
292
Ir(III)H(S) + Cl- Ir(III)H(Cl) + S
(110)
of oxidative addition of HCI indicate that Cl- adds first in a two-step ionic
process, (111) and (112).
Ir(I) + Cl- IrCI- (111)
IrCI- + H+ Ir(III)H(CI)
(112)
The effect of chelation in facilitating oxidative addition has been
studied(69) by comparing equilibrium constants for (113) and (114) (X = 0,
CO, and CO2, and As replaced P in some experiments). Kll'4/ Kl13 are of
the order of 10
3
_10
4
; Kl13 fall, X: CO
2
> 0 CO, but K1l4 decrease
CO > 0 = CO
2
. The equilibrium constants are affected by changing P to
As.
trans-[lrCI(CO)(PPh
3
h] + PhXH [lrH(XPh)(CO)(PPh
3
h] (113)
trans-[lrCI(CO)(PPh
3
h] + o-Ph
2
PC
6
H
4
XH
[IrHCXC6H4 PPh2-o)(CO)(PPh
3
)] + PPh
3
(114)
A measure of the thermodynamic stability of various Ir(III) compounds
has been obtained by Y oneda and Blake, (70) who have enthalpies
of oxidative addition of 1
2
, HI, and various alkyl and acyl iodides to
Ir(l) + RI ---. trans -Ir R (I) (or cis, if R = H) (115)
trans-[lrCl(CO)(PMe3h] in CH
2
CICH
2
Cl as in (115). From these enthal-
pies, relative values of bond energies, D(lr-R), can be estimated: R = H>
CH
3
- I - CH3CO > C2HS > Pr" > Pri > PhCH
2
. Enthalpy changes have
also been measured(71) for the oxidative addition of acetyl chloride to
trans -[lrCI(CO)L
2
] for various phosphines. These can be fitted satisfactorily
to two-variable equations containing Tolman's steric and an electronic
parameter. Values have also been found for the addition of other acyl
chlorides to the bis(PMe2Ph) complex, and the dissociation energy, D (Ir-
COCH
3
), is estimated to be 205 kJ mol-
1
.
A challenge is provided by the possibility of oxidative addition to a
nonactivated C[sp3]-H bond. Janowicz and Bergmann(72) have observed
that [(MesCs)(Me3P)lrH2] reacts with cyclohexane and with neopentane
photochemically (Amax 275 nm) to give [(MesCs)(Me3P)lr(H)(C6Hll)]
and [(MesCs)(Me3P)lr(H)(CH2CMe3)], respectively. They speculate that
the reaction proceeds by initial loss of H2 from the dihydride. Hoyano and
Graham(73) report stoichiometric oxidation addition by irradiation (Hg
vapor lamp) of [(MesCs)lr(COh] in the presence of neopentane or cyclo-
hexane, which yields [(MesCs)lr(CO)(H)(R)] (R = CH2CMe3 or C6Hl1)'
They assume that [(MesCs)lr(CO)) is an intermediate.
Milstein and Calabrese(74) have observed the first unassisted
oxidative addition of simple ep'oxides to transition metal complexes.
[(Me3P)4IrCI] reacts with RC(H)OCH
2
to give the compounds
[(Me
3
Ph(CI)Ir(H)CH
2
C( =O)R]. Intermediates containing groups such as
Ir+ -CH
2
CH(O-)R or IrCH
2
CH(O)R are suggested. A case where radicals
have to exist, occurs in the oxidative addition chemistry of Ir(I) and Pt(O)
compounds.(75) The diradical CF
3
N(O')CF
2
CF
2
N(O')CF
3
reacts with
[Pt(PPh
3
)4], for example, to give [(Ph3PhPtON(CF3)CF2CF2N(CF3)O].
11.3.4. Nickel, Palladium, and Platinum
11.3.4.1. Theoretical Treatments
Calculations(76) to find the transition state for the oxidative addition
of H2 to Pt(PH3h to give cis- [Pt(Hh(PH
3
h] indicate a C 2v geometry with
a P-Pt-P bond angle equal to 148
0
and an H-H bond length only 4%
larger than in free H
2
. The activation energy to reach this transition state
is only about 8 kcal mol-I. The pathway which would result in trans addition
is symmetry forbidden.
Three groups(77) have collaborated on a theoretical treatment of reduc-
tive elimination from d
8
complexes as in equation (116). In four-coordinate
(116)
complexes, cis-[L
2
MR
2
], elimination is easier the more and less (T donating
Rand L are, respectively. The energy of the d
xy
orbital (whose lobes are
directed towards the ligands) affects the ease of reductive elimination, so
that the process should be easier for Ni than for Pd and Pt, just as it is in
fact. In aT-shaped cis-[LMR
2
] system, elimination is again easier the more
donor R is. The corresponding trans -[LMR
2
] does not appear to eliminate
in practice; calculations indicate that the activation energy needed to
isomerize it to the cis form rises as R becomes more donor. Hence it
follows that if R is a poor donor, cis-trans isomerization should occur
more readily than reductive elimination. Whitesides' group(78) has also
tackled the question of reductive elimination in the same system, with
calculations on the starting complexes, [L
2
MX(Y)], where X and Y = H
and/or Me. Systems which eliminate XY readily have occupied molecular
orbitals with pronounced anti bonding character in the XMY region, but
these orbitals are vacant in compounds which do not react easily. Bonding
in the first case is predominantly covalent and in the second ionic, so that
less charge transfer occurs during reductive elimination in the first instance.
[L2NiMe2] and [L
2
PtH
2
] provide examples in the first category, [L2PdMe2]
and [L2PtMe2] in the second.
Theoretical studies(79) have also been made on nickelacyclopentane.
In practice the product of decomposition of such a compound, [LnNiJ,
depends on its coordination number, being, respectively, butene, cyclo-
butane, and ethene for (n + 2) = 3, 4, and 5. The theoretical studies show
that for planar four- and three-coordinate systems (viz. cis-[LzNiJ and
[LNiJ), the reductive elimination of cyclobutane is symmetry allowed, while
tHe production of ethene is not. The reverse is true for tetrahedral [LzNiJ.
Five-coordinate species, [L3NiJ, can give either cyclobutane or cyclobutane
and ethene depending on their shape.
11.3.4.2. Nickel
Oxidation addition to Ni(O) can lead to both Ni(II) and Ni(I) complexes,
as in equations (117) and (118), respectively. Morvillo and Turco(SO) have
[Ni(PCY3hJ + RX -4 [Ni(X)(R)(PCY3hJ + PCY3 (117)
[Ni(PCY3hJ + RX -4 [Ni(X)(PCY3hJ + R (118)
collected further evidence for these reactions and studied formation of
hydrocarbon products (Cy = cyclohexyl). If R is ethyl, ethane can be
produced by abstraction of hydrogen by R from hydrides (formed as
intermediates) or from toluene (the solvent), and from coordinated R
ligands (by cyclometallation of [Ni(X)(R)(PCY3h]). When R is phenyl,
biphenyl is produced via reaction (119).
2[Ni(X)(Ph)(PCY3)n] -4 + [Ni(X)(PCY3)nr + [Ni(X)(PCY3)"J (119)
Morvillo and Turco(S!) also looked at the oxidative addition of methyl
and ethyl halides to nickel(I) complexes, [NiX(PEhhJ, which is about ten
times faster than the first step of the same process for nickel(O) systems,
[Ni(PEt3)4] (X = Br or I). As some nickel(I) is formed in the second case,
an overall reaction scheme can be constructed which includes both oxidation
states, (120)-(124). Reactions (122) and (123) are slow and (124) is very
slow.
[Ni(0)L
4
J

[Ni(0)L
3
] + L (120)

[Ni(0)L
3
] + RX

[Ni(II)(X)(R)L
2
] + L (121)

[Ni(II)(X)(R)L
z
] -4 RH + Ni(II)
or -4 RR + [Ni(I)XL
3
J (122)
[Ni(I)XL
3
] + RX -4 intermediate (123)
intermediate -4 RH + Ni(II)
or -4 RR + [Ni(II)(XhL
2
] (124)
11.3.4.3. Palladium
Aryl iodides add cleanly to zero-valent Ph
3
P (or L) complexes of
palladium. The kinetics and activation parameters(82) support a simple
concerted oxidative addition process as in (126), preceded by (125). A
[PdL
3
] [PdL
2
] + L
[PdL
2
] + Arl --+ [Pd(I)(Ar)L
2
]
(125)
(126)
Hammett plot of rate constants, K 125k 126, for various Ar gives a p value
of 2.0, which is interesting being the value associated with the proposed
transfer of one electron in the analogous nickel system, namely, the first
step in (127).
Ni(0)L
3
+ Arl --+ {[Ni(I)L
3
],Ar(} --+ Ni(I) + Ni(1I) (127)
It has been confirmed(83) that the postulated (1j 3 -allyl) (acetate ) inter-
mediate can be observed when allyl acetates add oxidatively to Pd(O), e.g.,
(128).
[Pd{P(C
6
H
ll
hh] + CH
2
= CHCH
2
0Ac
--+ [(1j 3 -C
3
H
s
)Pd{P(C
6
H
ll
hh(OAc)] (128)
A paper by Yamamato's group(84) is important in providing examples
of intramolecular reductive elimination from cis -dialkyl palladium systems,
clarifying the chemistry of the trans isomers, showing the role of three-
coordinate intermediates, and in testing their predictions(77) (see Section
11.3.4.1). Thermolysis of various cis -[L
2
PdR
2
] compounds (L = phosphine)
yields at least 90% R
2
, in particular a mixture of cis-[(MePh
2
PhPd(CH
3
h]
and cis-[(MePh
2
PhPd(CD
3
h], giving very largely C
2
H
6
and C
2
D
6
without
scrambling. As free phosphine retards the process, it is postulated that
reductive elimination is intramolecular taking place from cis -[LPdR
2
], as
in (129) and (130); (cis-[PdEt2(dpe)] is exceptional). There is a contrast
with [NiMe2(bipy)] and [NiMe2(dpe)], reductive elimination from which is
not inhibited by free phosphine.
cis -[L2PdR2] cis -[LPdR
2
] + L
[LPdR2] --+ LPd + R2
(129)
(130)
The rate of reaction is increased by a fall in basicity of L (as predicted in
the theoretical(77) work) and by a rise in its cone angle. Elimination does
not occur from trans isomers. However IH nmr indicates reaction (131)
and scrambling experiments analogous to those above point to (132), which
trans-[L
2
Pd(CH
3
h] trans-[LPd(CH
3
h] + L (131)
296
trans-[LPd(CH3hJ + cis-[L2Pd(CD3hJ ---+
cis-[LPd(CH
3
)(CD
3
)] + cis-[L
2
Pd(CH
3
)(CD
3
)J (132)
together effect trans to cis isomerization, thus providing a pathway for
reductive elimination. (Thermolysis of the corresponding trans -diethyl con-
taining compounds gives C
2
H
6
and C
2
H
4
by (3 elimination. This reaction
is not retarded by free phosphine.) The trans to cis isomerization (132) is
catalyzed by lithium alkyls. The equilibrium seems to be influenced by both
steric and electronic factors. The latter would be expected from the theoreti-
cal work.
Studies by Moravskiy and Stille(85) on the rate of elimination of ethane
from cis-[(MePh2PhPdMe2J (as above) in different solvents sheds further
light on the mechanism. Although the rates are almost equal at 60C, there
are large variations in the activation parameters which suggest that polar
solvents coordinate to the palladium in the transition state. In the same
paper(85) parameters were also obtained for an overall process (133) involv-
ing addition of Mel to Pd(II) to give Pd(IV) from which elimination of
ethane occurs.
[Me2Pd(PMePh2h] + Mel ---+ [Me3(I)Pd(PMePh2h]
---+ [Me(I)Pd(PMePh
2
h] + Me2 (133)
Cis- and trans-[(Ph
3
PhPdMe(E- and Z-CH=CHPh)) eliminate to
give E- and Z-MeCH=CHPh. Product analysis from decomposition of
the cis-E isomer in the presence of deuterated resonance material suggests
an intramolecular mechanism.(86) Nuclear magnetic resonance points to the
presence of alkene species, e.g., (1l2-PhCH=CHMe)PdL, while the effect
on rate of free phosphine and of the alkene product suggest other inter-
mediates.
11.3.4.4. Platinum
The rates of oxidative addition of methyl iodide to various tris- and
bis(phosphine) (L) complexes have been measured in benzene at 25C
[PtL
4
] [PtL
3
] + L [PtL
2
] + 2L
[PtL
3
] + Mel ---+ [PtI(Me)(Lh]
[PtL
2
] + Mel ---+ [PtI(Me)(L)z]
(134)
(135)
(136)
[equations (135) and (136)] [after allowing equilibrium (134) to be estab-
lished].(87) Rate constants are 4 to 5 times smaller for the tris compounds,
and for both bis and tris rise in the sequence, L = P(C6H4Et-p h <
P(C
6
H4Me-pb < P(n-C
I6
H
33
b < P(n-CgH
17
b. [Pt(PPh
3
hJisanomalousin
showing an induction period.
[Pt( 11 2 -C
2
H
4
)(PPh
3
hJ and SnMe3Ar appear to react(88) through steps
(137)-(139). The last two reactions probably involve oxidation addition
[Pt(C
2
H
4
)(PPh
3
hJ + SnMe3R -+
cis-[PtR(SnMe3)(PPh3hJ + C
2
H
4
(137)
cis -[PtR(SnMe3)(PPh3hJ + SnMe3R
cis-[PtR(SnMe2R)(PPh3hJ + SnMe4 (138)
cis-[PtR(SnMe2R)(PPh3hJ + SnMe3R
cis-[PtR(SnMe3)(PPh3hJ + SnMe2R2 (139)
(as the first does), but no intermediates are observed. The rate of (137)
rises with increase in electron-withdrawal power of R, or p-X-C6H4' viz.,
X: NMe2 < OMe < H < F < N02, which suggests a significant amount of
carbanion character in R in the transition state.
The internal oxidation addition reaction(89) involving the rearrange-
ment of [Pt(0)(PPh
3
)z{ 1J
2
-(RShCSO}] to cis-[Pt(II)(SR)(RSCSO)(PPh
3
)ZJ
has been shown to be intramolecular (R = Ph or C
6
H4Me-p).
The thermal decomposition of various dialkylbis(phosphine)-
platinum(II) complexes in cycIohexane to give platinacycIobutanes, pen-
tanes, and hexanes has been studied by Whitesides' group. (90) The reac-
tions are retarded by free phosphine, L, indicating (140), while activation
(140)
parameters are similar even when different-sized rings are formed, which
suggests that cyclization, (141), occurs before the rate-limiting step (142)
[LPtR
2
J [H(L)(R)i>t='R-
H
(141)
(Pt-R-
H
denotes a platinacycIoalkane group.) If activation parameters are
taken as a measure of free energies of formation, it follows that the strain
energies in the four-, five-, and six-membered rings differ by 4 kcal mol-
1
or less.
An investigation has also been made of the thermal decomposition
of various platinacycIobutanes in cycIohexane.(91) That of
[(Et
3
PhPtCH
2
CMei:H
2
J is heterogeneous, becoming homogeneous in
the presence of mercury. Those of the corresponding and (C6H
ll
hP
complexes are homogeneous, yielding 1, 1-dimethylpropane, the [bis(phos-
phine)platinum(O) complex, and a little neopentane; Ea and log A are
46 3 keal mol-
1
and 23 2, and 42 2 kcal mor
l
and 21 1 in these
two instances. The large values of log A suggest the reductive elimination
of the cyclopropane is rate limiting. In the case of the complex, free
phosphine retards the reaction, while deuteration of the Pr
i
groups has no
effect on the rate. Two mechanisms are proposed for the homogeneous,
uncatalyzed processes. The first, (143) and (144), is straightforward, the
[L
2
PtCH
2
CMel:H
2
) [LPtCH
2
CMei:H
2
) + L (143)
[LPtCHzCMei:HzJ ---+ [CHzCMei:Hz) + LPt(---+ LzPt) (144)
second step being rate limiting. The second scheme proposes (143), followed
by oxidative addition of a C-H bond of one of the phosphines to the
platinum in a cyclometalation reaction, (145), and then by the reductive
elimination step, (146). Some HID isotope effect might then be expected.
[LPtCH
2
CMez<':H
z
) [R
z
(R-
H
)PPt(H)CH
z
CMei:H
2
) + L (145)
---+ CH
2
CMe
z
CH
z
+ [Rz(R-HWPtH)(---+ ---+ LzPt) (146)
This piece of work and the last provide a contrast since a platinacyc-
lobutane ring is formed in one and destroyed in the other, but there is no
indication of reversibility between the systems. Thermodynamic consider-
ations suggest that reversibility is not observed because of significant
decreases in free energy in the hypothetical equilibria, (147) and (148).(911
[L2Pt(CHzCMe3hJ [L
z
PtCH2CMezCHzJ + CMe4 (147)
[L
2
PtCH
2
CMezC:H
z
J LzPt + CHzCMei:H2 (148)
Platinacyclobutanes eliminate cyclopropane in the presence of iodide
or thiocyanate (or Y-) in methyl cyanide solution. Kinetic studies(9Z) suggest
a mechanism consisting of reactions (149)-(152), the last being rate limiting.
[L2(X)2P<)<1 [L(X)2Pt0<1 + L (149)
[L(X)2Pt0<1 + Y- [L(Xh(Y)Pt0<l- (150)
[L(X)2Pt0<1 + M+Y- [L(Xh(Y)Pt0<l- + M+ (151)
[L(XMY)Pt0<]- -----+ [LX
2
(y)ptr + [>< (152)
Y has to become a ligand before Pt-C bond fission can occur. As three
pre equilibria are involved, it is not surprising to find that the rate is affected
by cations and by potential ligands such as pyridine and DMSO. The rate
of elimination is lowered by methyl groups on the propane moiety.
Dialkylplatinum compounds and platinacyclobutanes can also decom-
pose not by reductive but by {3 -hydrogen elimination. Kinetic and hydro-
gen/deuterium scrambling experiments on the thermal decomposition of
[(EhPhPtEtzJ in cyclohexane to [(EhPhPt] and ethane suggests reactions
(153) to (157).(93) At low, medium, and high concentrations of free phos-
phine (L), (153), (155), and (157), respectively are rate limiting. Inciden-
tally, none of these steps involves (3 -hydride elimination, which occurs in
[L
2
Pt(C
2
H
s
hJ [LPt(C
2
H
s
h] + L (153)
[LPt(C
2
H
s
h] [LPtH(C2Hs)(112-C2H4)] (154)
[LPtH(C2Hs)(112-C2H4)] [LPt(112-C2H4)] + C
2
H
6
(155)
[L
2
Pt(C
2
H
s
h] [L
2
PtH(C
2
H
s
)(11
2
-C
2
H
4
)] (156)
22
[L
2
PtH(C
2
H
s
)(11 -C
2
H
4
)] [L
2
Pt(11 -C
2
H
4
)] + C
2
H
6
(157)
the product-forming reactions (155) and (157). Increasing disordering is
reflected in the entropy terms: = 3, + = 12, and +
+ = 35 cal mol-
1
K-
1
The three-coordinate intermediates,
[(EhP)Pt(C
2
H
s
h], can change shape rapidly. (94) The pathways for
decomposition of the corresponding di(cyclo-butyl and -pentyl) complexes
are the same, but that of the di(cyclopropyl) system is more complicated. (9S)
The thermal decomposition of some bis(acetonitrile) and
bis(pyridine )platinacyclobutanes have also been studied. Cushman and
Brown(96) have found that the organic products formed in the thermal
decomposition of various compounds in which the ring is alkyl substituted
are ole fins or ylides, depending whether the inert ligand, L, is acetonitrile
or pyridine. They rationalize the products in terms of a sequence of
reactions: loss of one L ligand, skeletal isomerization of the platinacyc-
lobutane so that the platinum is bonded to the most substituted carbon,
then {3 -hydride elimination to produce an alkylplatinum(IV} hydride from
which either the olefin is produced by reductive coupling or the ylide is
formed.
An example of reductive elimination from a bimetallic system is
provided by the work of Hill and Puddephatt(97) on the mechanism of
reductive elimination of H2 from a binuclear platinum system, equation
(158). Mixtures containing de ute rated starting material give no HD, no
[HPt(IL-H)(IL-dppmhPtHt + L [HPt(lL-dppmhPtLt + H2 (158)
intermediates can be detected, the process is first order in each reactant,
and a large HID kinetic isotope effect is observed. k(21C) = 10.9 and
1.60 M-
1
s -1 for L = dppm and PPh
3
. Qualitatively it was observed that
use of smaller phosphines resulted in more rapid elimination of H
2
. The
results point to a one-step reaction with a transition state in which there
is some association and considerable lengthening of Pt-H bonds.
11.3.5. Actinides
The first oxidation additions studies on organoactinides have been
described. (98) Alkyl halides react with [(MesCshUCI] in benzene some
10
4
_10
7
times faster than with analogs such as the [Cr(II)en2f+ and the
B 12r systems. Comparison of rates of reaction of RCI for various R with
this complex and with the atom abstractor, Bu3Sn", together with the
formation of some R
2
, RH, and olefin as by-products indicate an SH2
halogen atom abstraction prQcess. From the starting THF complex, reac-
tions (159)-(161) are proposed.
[(MesCshUCI(THF)] [(MesCshUCI] + THF (159)
[(MesCshUCI] + RX -+ [(MesCshUCI(X)] + R (160)
R" + [(MesCshUCI] -+ [(MesCshUCl(R)] (161)
Chapter 12
Reactivity of Coordinated
Hydrocarbons
12.1. Introduction
As in the previous volume, this chapter reviews kinetic and mechanistic
studies of the stoichiometric reactions of coordinated hydrocarbons with
nucleophiles and electrophiles, together with some related processes such
as cycloadditions. Nucleophilic addition and substitution, in particular,
continue to attract considerable interest, especially with dienyl- and arene-
metal substrates. Even here, however, quantitative studies still lag far
behind the extensive synthetic literature. However, fundamental reactivity
patterns and parameters are beginning to emerge from the mechanistic
studies which should assist in the design of rational syntheses.
Related catalytic processes are discussed elsewhere (Chapter 14), as
are intramolecular ligand rearrangements (Chapter 13).
12.2. Nucleophilic Addition and Substitution
12.2.1. u-Bonded Hydrocarbons
Several kinetic studies of nucleophilic attack upon coordinated car-
benes have appeared. Particularly revealing has been a stopped-flow investi-
gation(l) of the addition of PBu; and P(OBu"h to the carbene carbon in
the chromium triad carbenes, [M(COhCR'(OEt)] (M = Cr, Mo, or W;
R' = Ph or Me) [equation (1)]. The forward rate constant, kh is little
301
302 12 Reactivity of Coordinated Hydrocarbons
OEt
/
(CO)sMC + PR
3
"-
R'
OEt
/
(CO)sM-C-PR3
"-
R'
(1)
influenced by steric factors associated with either the nucleophile or the
metal. In contrast, both the reverse rate constant, Lb and the equilibrium
constant exhibit marked steric effects. These observations suggest little
P-C bond formation in the transition state for the addition process. They
are also inconsistent with initial attack at the metal followed by subsequent
migration to the carbene ligand. The addition rate constant, k 1, varies with
the metal in the order Mo > W > Cr (8.5: 5.7: 1), which is somewhat
different to the order previously observed(2) for addition to the
7T-hydrocarbon ligand of [M(COhC1J-C7H7W cations (Cr> Mo - W;
2: 1 : 1). Another significant difference between the metal-carbene and
metal-tropylium substrates is the markedly different k
PBu
) kp(OBub ratios
(30 and 5000, respectively). These organometallic processes therefore
clearly do not conform to Ritchie's(3) electrophile-independent equation
for free organic electrophile-nucleophile combinations.
The rate law (2) has been established(4) for the reactions of the
rate = kobs[complex], (2)
dithiocarbene complexes [W(CO)s{C(SMe)z}] with tertiary phosphines to
yield the phosphorane species 1, and with PHPh
2
to form the phosphine
complex 2. Rate-determining attack by the phosphine on the car bene
MeS"
C=PR
(COl w-S/ 3
5 "Me
1 2
carbon was proposed in each case, followed by rapid rearrangement.
Support for this mechanism came from the decrease in k with decreasing
basicity and nucleophilicity of the phosphines (PEt
3
> PMe2Ph -
PMePh
2
> PHPh
2
> P(OMeh). Related processes occur with cyclic
dithiocarbene tungsten complexes (n = 2-4).
Reactivities increase markedly with increasing ring size. This was attributed
to the greater flexibility of the larger rings allowing release of steric
hindrance as the phosphine ligands approach.
Synthetic and spectroscopic studies also support the transitory forma-
tion of related ylide complexes 3 in the reactions between amines and the
carbene complexes [FeCp(CO)z{C(XR)(YR)}].(S) The reactivity of the
12.2 Nucleophilic Addition and Substitution
XR
[CPICOIZ 1
3
303
ylide intermediate is controlled by the relative leaving-group abilities of
the carbene substituents XR and YR. In the reaction with piperidine these
decrease in the order PhSe- - PhS- > PhO- > MeS- > MeO-.
In contrast, kinetic studies(6) of the reaction between
[Cr(CO)s{C(Ph)OMe}] and various arylalkynes to give [Cr(COh(7J
6
-
substituted-l-naphtho!)] complexes indicate initial CO ligand loss to form
a steady state concentration of [Cr(CO)4{C(Ph)OMe}], followed by addition
of the alkynes to the metal. The subsequent rearrangements, involving
attack at the carbene, to give the naphthol products are rapid.
Nonparametrized Fenske-Hall molecular orbital caiculations(7) on the
carbyne complexes trans-[CrX(CO)4(CR)] (X = CI, Br, or I; R = Me, Ph,
or NEt
2
) support an earlier contention that nucleophilic additions to carbyne
ligands are frontier orbital controlled rather than charge controlled. Thus,
the only such complex to undergo nucleophilic addition to its carbyne
carbon atom, namely, trans-[CrBr(COMCC
6
H
4
Me-p)], is the only one
whose LUMO corresponds to a Cr-carbyne 1T-antibond.
The methyl hydrogens in the tri-IL -phenoxo complex
[{Rh(CsMes)h(OPhh][(PhO)sH4] exchange moderately quickly (t1/2-
40 min at 20C) with deuterium in eH
6
] acetone solution. (8) A mechanism
was proposed involving formation of the enolate complex 4, followed by
transfer of a methyl hydrogen to the metal to form a fulvene-rhodium
hydride species 5 from which the H can be eliminated by transfer to enol ate
to give coordinated acetone.
4
12.2.2. 1r-Bonded Hydrocarbons
12.2.2.1. Addition at Monoolefins, Alkynes, and Allenes
The widely observed activation of ole tins toward nucleophilic attack
via coordination to transition metal centers has long been qualitatively
attributed to electron withdrawal by the metal. However, a recent theoreti-
cal analysis(9) suggests that symmetrically 1/ z -coordinated olefins should in
fact be deactivated toward nucleophiles. The novel suggestion was made
that the crucial requirement for olefin activation (except in dlO MLz systems)
is slippage of the metal along the olefin 7T bond to form an intermediate
resembling 1/ 1 coordination, i.e., 6 -. 7. Such a deformation leads to stabiliz-
ation and increased localization of the fragment ligand LUMO (7T*-Ab
z
),
'- ,-
'- ,-
jl\'
MLn
6
-
'- ,-
'- /
j I'"
MLn
7
resulting in greatly increased overlap population in its interaction with the
nucleophile HOMO. Experimental support for this proposal has come from
kinetic studies(1O) of the reactions of 8a (R = H) and 8b (R = OMe) with
the soft nucleophile 9 to give 10. An X-ray structure of the vinyl ether
@$
I
Fe R
c61Y;
CO
8
@
I

CO I
CO
9
@$
I R
/'" Fe" "- J.
CO I ;, 'V' ']
CO Fe(012
I
@
10
complex 8b showed it to have an unsymmetrically bound 1/ z -olefin, and it
was found to be 530 times more reactive (at -3C in CD
3
N02) than the
undistorted parent cation 8a. In the absence of other electronic effects,
replacement of a vinyl hydrogen atom in 8a by a MeO substituent would
be expected to cause reduced reactivity.
The regiochemistry of nucleophilic addition to coordinated olefins can
also be rationalized by this slippage hypothesis. With vinyl ether 7T com-
plexes of type 8b nucleophiles add regiospecifically at the carbon bearing
the donor substituent. (11) It was pointed out that donor substituents should
facilitate slippage away from the substituent (as observed crystallographi-
cally for 8b), leading to the correct intermediate for the observed
regiochemistry. Similar regiospecific Markownikoff addition of amines to
the coordinated ole fins in the complexes [PtClz(am)(1/2-CH2CHR)]
12.2 Nucleophilic Addition and Substitution 305
(R = Me, Et, or Ph) has been observedY2) In contrast, with electron-
withdrawing olefin substituents (R = CN or COOMe) amine addition occur-
red at the carbon atom remote from the substituent [equation (3), 0-0 =
acac]. Similarly, an X-ray structural study(13) has confirmed that addi-
tion of Me- to the '112-alkyne ligand in [Fe(COh('11-Cp)-
('112_MeC=CC0
2
Et)]BF
4
occurs at the carbon away from the electron-
accepting COOMe substituent. The regioselectivity of amine addition to
the allene ligand in cis-[PtC}z(PPr3)(CH2=C=CH2)] has also been investi-
gated,(14) addition being specific to the terminal (methylene) carbon.
CI
1
)I-Pt-O + am
R 6..J
CI
1
amCH
2
CHR-Pt-0
I,.}
o
(3)
An interesting example of temperature control over chemispecificity
is the reaction of [RuC}z(CO)(PMe
2
Phh('11-C
2
H
4
)] with PMe2Ph.(15) At
35C, olefin replacement is observed. However, at 6C the kinetically
favored product was the cation [RuCI(CO)(PMe
2
Phh('11 1_
CH2CH2PMe2Ph)r, believed to be formed via initial nucleophilic attack
on the ethene ligand.
12.2.2.2. Addition at '11 3 -Enyls
A 1H nmr spectral analysis of the diene derivative from the reaction
of complex 11 with the potassium enol ate of acetone (in the presence of
excess PPh
3
) showed(16) it to have the structure 12. Thus, in common with
OMe
Lfd'H
Pd
/ 'X2
MeCOCH2 X / OMe

11 12
previous additions of malonates and amines, the enol ate nucleophile adds
from the face of the 7T-cyclohexenylligand opposite to the palladium. In
contrast, reactions with hydride ion or phenyl carbanion have been shown
to occur via initial attack at the metal.
12.2.2.3. Addition at 1/ 4 Dienes
In the first quantitative study of nucleophilic attack upon coordinated
cyclobutadiene, Choi and Sweigart(17) have reported kinetics for reactions
(4) in nitromethane, using a wide range of spectator ligands (L) and various
phosphorus nucleophiles (PR
3
). All the reactions obeyed equation (5), as
[Q}$
I
Fe ((Ol(NOlL
13
+
(4)
14
(5)
expected for equilibrium processes. The absence of kinetic or spectral
evidence for an intermediate, and the known exo configuration of the
phosphonium ring adducts 14, indicated direct addition by PR
3
to the
cyclobutadiene ring. The electrophilicity of the cyclobutadiene ligand in
(13) varied considerably with the nature of L, kl decreasing by a factor
of 100 down the series
L = CO> P(CH
2
CH2CNh - P(4-CIC6H4h > P(4-FC
6
H4h > AsPh
3
- PPh3 > SbPh3 - P(4-MeC6H4h > P(4-MeOC6H4h.
The nucleophilicity of the phosphines followed the order:
P(4-MeOC6H4h > P(4-MeC6H4h > PPh
3
> P(CH
2
CH
2
CNh > P(OBunh.
This series correlated with Tolman's X scale, and the tri(aryl)phosphines
also gave a good Hammett correlation. A two-point Br0nsted plot for PPh
3
and P(4-MeOC
6
H4h adding to 13 (L = PPh
3
) showed a slope of 0.47,
indicating the importance of nucleophile basicity. Furthermore, the slope
of 0.36 found for a rate-equilibrium plot for reaction 4 (L = PPh
3
) suggested
that bond formation and Sp2 to Sp3 rehybridization are approximately one
third complete in the transition state for the forward (k
1
) additions.
12.2.2.4. Addition at 1/5-Dienyls
Kane-Maguire et alys-22) have described synthetic and kinetic studies
of the reactions of the dienyl cations [Fe(COh(1-5-1/ -dienyl)t (dienyl =
C6H7, 2-MeOC6H6, C7H9) with a range of amine, phosphine, and aromatic
nucleophiles. Substituted pyridines react in CH
3
CN to give exo -pyridinium
adducts, e.g., equation (6), and provide an ideal series for examining
15
electronic and steric contributions to amine nUc1eophilicity. (18) The general
rate law (7) was observed, except for the equilibrium reaction of 15 with
3-cyano-pyridinine, which obeyed equation (8). For attack of sterically
rate = k[Fe][amine]
rate = k1[Fe][amine] + k-1[Fe]
(7)
(8)
noncrowded pyridines (X = H, 3-Me, 3-CN, 4-Me, 4-Ph, or 3,5-Me2) on
15, a linear Brf/Snsted plot of log kl vs. pKa of the amine conjugate acid
(in water) was found. Its high slope established a strong dependence of
rate on amine basicity. Successive blocking of the 2- and 6-positions of
pyridine by methyl groups caused marked nonadditive steric retardation
(e.g., 2,6-dimethyl pyridine is -10
4
times less reactive toward 15 than
noncrowded pyridines of the same basicity). The rate trend C
6
H7 >
2-MeOC
6
H6> C
7
H9 observed with several pyridines supported direct
addition to the dienyl rings.
A similar dienyl dependence (C
6
H
7
> 2-MeOC6H6 > C
7
H
9
) was found
for the related reactions with substituted anilines, again indicated direct
exo additionY9,20) These latter processes were shown to occur in two steps
Scheme 1
x
[
J

A
+
in CH
3
CN, as shown in Scheme 1 (A = H or OMe; n = 1 or 2). For the
reactions of 4-methoxy- and 4-methyl-aniline with 15, which proceed to
completion, rate law (7) was followed. However, for the equilibrium reac-
tions of the other less basic anilines, the two-term expression (9) was
. k-
1
[H+]
kobs = k
1
[amme] + [H+] + K2
K
a
(9)
obeyed. For attack by nonsterically hindered anilines on [Fe(COh(1-5-T/-2-
MeOC6H
6
)t, a BrJ1lnsted plot of log k 1 vs. pKa had a slope of 1.0, confirming
a very marked dependence of kl on basicity. An excellent Hammett
correlation was also observed with a slope of -2.7, indicating significant
bond formation and build-up of positive charge on the aniline nitrogen
atom in the transition state. The steric retardation of k 1 caused by blocking
substituents in the 2-position of the anilines was considerably smaller than
that found previously for the addition of pyridines.
In a related study(21) of triarylphosphine, P(XC
6
H
4
h, addition to the
dienyl ring of 15, rates varied with X in the order 2-MeO > 4-MeO >
4-Me > H > 2Me (relative rates 90/9/4/1/10-
3
). The unexpectedly rapid
reaction with P(2-MeOC
6
H4h was rationalized in terms of stabilization of
the transition state 16 via an an chimeric effect involving overlap between

((0)3
Fe
/()
16
the filled 2p orbital of the 2-MeO oxygen and the empty phosphorus 3d
orbital (only one aryl group is shown for clarity). This anchimeric effect,
quantified by the k(2-MeO)/k(H) ratio of 91, is considerably larger than
that previously observed for addition of arylphosphines to benzyl chloride,
suggesting a greater degree of phosphorus-carbon bond formation in the
transition state for attack on 15. Also unexpected was the report by Brown
et ai.(22) that the phosphines PEh, PPr;, PBu;, and PMe2Ph react with the
cycloheptadienyl cation [Fe(COh(1-5-T/-C7H9)r in CH
3
CN to give endo-
phosphonium adducts. This behavior contrasts with that in dichloromethane
solvent where only the exo adducts are formed. Tertiary phosphines with
more than one phenyl substituent did not yield endo products, presumably
because of steric inhibition. Although the authors favored initial attack at
the metal for the path leading to endo products, direct endo addition seems
equally probable, and other studies(23) indicate that endo addition is pre-
ceded by more rapid, but less thermodynamically favorable, exo attack.
Brown's report(22) provides a further important instance of endo attack,
emphasizing once more the dangers inherent in the widespread earlier
assumption of exclusive exo addition to coordinated dienyl groups.
The cation 15 has also been shown(24) to act as an electrophile toward
a variety of methoxy-benzenes to give novel diene-substituted aromatic
species 17 according to equation (10) (ArH = 1,3,5-trimethoxy-, 1,2,3-
trimethoxy-, 1,2,4-trimethoxy-, 1,3-dimethoxy-, or 1,4-dimethoxy-
benzene). For each reaction in CH
3
N0
2
the rate law (11) was established.
15 + ArH -+ [Fe(COh(Ar.C
6
H
7
)] + H+ (10)
17
k
2
K
1
[complex][ArH]
rate = 1 + K1[ArH]
(11)
This was interpreted in terms of the electrophilic substitution mechanism
outlined in Scheme 2, involving rapid pre equilibrium formation (K 1) of a
7T complex, followed by rate-determining rearrangement (k
2
) to a Wheland-
type u-complex intermediate 18. Rapid proton loss then leads to products
17.
Scheme 2
[(frFe(C0l3ff> +
b
K1
---'--"
1T'-complex
..---
15
SlOW) k,
[
-H+

[ X : Fe (CO)3J
fast
18
The quantitative influence of dienyl ring substituents on the reactivity
of [Fe(COh(1-5-1/-XC
6
H6)t cations has been comprehensively evaluated
for the first time using pentane-2,4-dione as nucleophile.(2S) In CH
3
N0
2
solvent, rates decrease in the order X = 1-C0
2
Me > 3-MeO > H >
3-Me> 1-Me - 2-Me > 2-MeO (reI. rates 10.4: 1.4: 1: 0.65: 0.37: 0.35:
0.16). Particularly interesting is the slight accelerating effect of a 3-MeO
substituent compared with the well-known inhibitory influence of a 2-MeO
group. The position of nucleophilic attack was not universally specified in
the above study. However, the influence of substituent nature and position
on the regiochemistry of such processes has been the subject of much study
(see Ref. 26 for a review).
A recent fascinating report indicates that regioselectivity in reactions
(12) [R = Et or C
2
H
4
C0
2
Me; Nuc = the stabilized enolates
+
+
NUC
-
19

1.0 R +
MeO
Fe ((0)3
20
NUCYyR

Fe((OS
21
(12)
-CH(C0
2
Meh and -CH(COMe)(C0
2
Me)] can be considerably modified
by changing the enolate countercation. (27) For example, in the reaction of
19 (R = C
Z
H
4
C0
2
Me) with -CH(C0
2
Meh, the product ratio 20/21 in
THF increased from 2.1 to 5.7 as the enolate countercation was changed
through the series Li+, Na+, K+. In the light of these observations, it was
proposed that the regioselectivity of nucleophilic addition to unsymmetrical
dienyl complexes such as 19 was under overall frontier orbital control,
superimposed upon which were more subtle effects arising from steric
demands of the substituents, coulombic interactions, and a "secondary"
orbital controlling effect. The choice between C(1) and C(5) as the site for
attack is apparently decided on coulombic grounds for non associated eno-
lates (K+ countercation). On the other hand, for associated enolates (Li+
countercation) the reduced nucleophile charge increases the importance of
frontier orbital interactions, favoring attack at C(1).
The regioselectivity of reduction of [Fe(COh(1-5-1/ -2-MeC6H6)t (22)
by NaBH
4
, LiBH4' LiEt3BH, and has also been examined.(28)
By analogy with the recent suggestion(9) that activation of coordinated
olefins arises from partial displacement of the metal-ligand bonding system
toward one terminus in the transition state, competing transition states of
the types 23 and 24 were proposed for nucleophilic attack on unsymmetrical
cations such as 22. As has been pointed out earlier,(29) charge distribution
in the starting dienyl cation does not explain the regioselectivity. Instead,
12.2 Nucleophilic Addition and Substitution

ri"I1 Fe(COl3

22

NU'--O
23
NU(t, ,M
" R

24
311
the thermodynamic stabilities of the alternative 1/ 4 -diene products, steric
effects of substituents, and the mechanism of addition were considered(28)
to be important.
The importance of the intimate mechanism was further emphasized
by the unexpectedly low stereoselectivity observed in the reduction of 22
by superdeuteride, LiEhBD. A 55/45 mixture of endo/exo reduction
products was obtained, in contrast to most other nucleophiles (including
LiBD
4
) which stereospecifically yield exo products. Presumably, with the
highly reactive trialkylborohydride reagents initial hydride attack occurs
at a CO ligand, giving a Fe-CHO intermediate, followed by transfer to the
dienyl ring. A similar mechanism has recently been proposed(30) to explain
the stereochemistry of reduction of acyclic dienyl cations.
Further papers have appeared outlining the resolution of chiral cations
such as 19 (R = H or Me), their conversion to optically active tricarbonyl
(1/ 4 -cyclohexa-l ,3-diene )iron(O) derivatives, and the assignment of absolute
configurations in some cases. (31,32) Of particular relevance to this chapter
are reports(33,34) of significant chiral discrimination during the additions of
both (R)-( + h89-1-phenylethylamine and (S,S)-( - h89-0- phenylenebis(1 ,2-
methylphenylphosphine) (25) to the dienyl ring of racemic (2R,2S)-
[Fe(COh(1-5-1/-2-MeOC
6
H
6
)t (19) (R = H). Recovery of unreacted
dienyl salt from reactions involving a deficiency of nucleophile provided a
convenient route to optically active 19 (R = H), whose circular dichroism
spectrum was reported for the first time. In reaction (13) using a two-fold
t-:1e
\ ,P'Ph
((
p..
(2R.2S)-(19. R = H) + I
::".. p'

Ph Me
25
-

(j/P"V
P
MeOr
Fe (COl
3
26

N
P
-
P
+ I
MeO ,'''';;
I
Fe(COl
3
27
(13)
excess of 19, the diastereomers 26 and 27 were formed in a ratio of -60/40
(by 'H nmr) in CD
3
CN or CD
3
COCD
3
solvent.
12.2.2.5. Addition and Substitution at Arenes
Detailed kinetic studies have been reported(3Sl for the substitution of
the halide group in complexes 28 (M = Cr, X = CI or F; M = Mo, X = F),
29 (R = H, X = CI or F; R = 2-Me or 4-Me, X = CI), and 30 (R = H or
Q-x
I
M(COI3
28
R $
O:x
I
Fe
@
29
@

I
Mn(C0l3
30
Me) by methoxide ion in methanol. In general, 7T complexation of the
halogenoarenes to the MLn units resulted in marked enhancement of
reactivity toward nucleophiles, activation decreasing in the order
Mn(CO); > FeCp+ Mo(COh > Cr(COh. For a given (7T-arene) metal
system, the reactivity of the halogenoarene ligands also generally decreased
through the series C6HsF > C6H
s
CI > MeC6H
4
Cl. In the case of the neutral
substrates 28, the simple rate law (14) (X = MeO) was obeyed. This
rate = k[complex][X-] (14)
observation, together with the much greater reactivity (-500 times) of
[Cr(COh(7]-C
6
H
s
F)] compared with the chloro analog, supported an addi-
tion-elimination mechanism (Scheme 3) involving rate-determining forma-
tion (k
1
) of a steady state concentration of a Meisenheimer-type anionic
intermediate (31).
Scheme 3
X OR
[M(COh(7]-C
6
H
s
X)] + RO-
X. 31
In contrast, with the cationic substrates 29 and 30, plots of kobs vs.
[MeO-] were curved.(3Sl This more complex behavior was rationalized in
Scheme 4
k'f / 32
/+MeO-
X OMe
[cPFe-Q]
1
[CpFe(1/ -C6HsOMe)r
terms of the mechanism illustrated in Scheme 4 for cation 29. Here
preequilibrium formation (K 1) of an ion pair 32 occurs, and the products
result from the competing reactions of MeO- with both the "free" cation
and the ion pair. The rate expression (15) is predicted for this mechanism,
k _ k
2
[MeO-] + K
1
kT[MeO-]2
obs - 1 + K
1
[MeO ]
(15)
in keeping with observation. Analysis of the data yielded ion pair constants
in the range 100-150 liters mol-I. Comparison of k2 and kT values showed
that ion-pairing substantially (-20-fold) reduces the reactivity of the arene
ligands toward nucleophiles.
Interestingly, a brief note by Litvak et al. (36) on the analogous reactions
of 29 (X = CI, R = 2-Me, 3-Me, 4-Me, 4-C0
2
Na, or H) with MeO- in
methanol reported simple second-order kinetics. In the absence of experi-
mental details, it is possible that the latter authors employed too narrow
a concentration range of [MeO-] to observe behavior (15). For the related
substitution of chloride from 29 (X = CI, R = H) using piperidine, the rate
law (16) was found to hold in a range of solvents. (37) The second-order
dependence on piperidine concentration was attributed to its catalysis of
the dehydrochlorination of an intermediate (J' complex.
rate = k[complex][piperidine]2 (16)
Rate and activation parameters have also been obtained for MeO-
substitution of the chloro group in the bis( 1/ -chlorobenzene )chromium
cation 33, as shown in equation (17).(38)
314
Q-Cl
I +
Cr
O-Cl
33
NaOMe
MeCN/MeOH
(9/1)
12 Reactivity of Coordinated Hydrocarbons
+
Q-OMe
I +
Cr (17)
O-OMe
The first quantitative information on the addition of anions to coordin-
ated cyclic 1T' hydrocarbons has appeared, namely, for attack by OH- and
CN- on [Mn(COh(T/-C
6
H
6
)t [equation (18) (X = OH- or CN-)],(39) The
X
+ X- [O-Mn(COhJ (18)
reaction with OH- in water obeyed rate law (14) (X = OH), giving a kOH
value of 290mol-
1
dm
3
s-
1
at 20.0C and ionic strength 0.25moldm-
3
.
An analogous process with NaCN in water fitted the two-term expression
(19), giving a keN value of 0.8 mol-
1
dm
3
S-I. Interestingly, attack by N3
(19)
on [Mn(COh(T/-C
6
H6)t was too rapid to follow by stopped-flow spec-
trometry, indicating the overall rate trend N3 OH- CN-. This unusual
nucleophilicity order, unexpected on the basis of both basicity and polariza-
bility, is similar to that previously observed for anion addition to free
carbonium ions.
Rose et al. (40,41) have examined the regioselectivity of addition of the
carbanion -CH(CH
3
)CN to the ortho-disubstituted arene 34 when coordin-
ated to Cr(COh or FeCP+ units. In the former case addition is fairly
regioselective. The major product (74%-79%) after oxidative removal of
the metal corresponded to attack at an arene carbon atom which is eclipsed
with respect to a carbonyl group of the Cr(COh unit of the most stable
conformer. (40) In contrast, carbanion addition to the arene when attached

R I R
R R
Ir <f)
/Ir"
/\
ceJ
I \ I I
34 3S 36
to the FeCp + moiety is nonselective, giving a mixture of isomeric prod-
ucts. (41) An interesting exception to the rules of Davies, Green and
Mingos(42) for predicting chemoselectivity in such reactions, is the report(43)
that hydride ion adds to the cations 35 (R = H or Me) to give exo-
cyclohexadienyl products 36. The guidelines would predict preferential
attack at the "open" cycloocta-l,5-diene (1,5-COD) ligand rather than at
the "closed" arene. This result is in keeping with previous observations(44)
of low electrophilicity for 1,5-COD when coordinated to Rh(I) and Ir(I)
[in contrast to its behavior on Pd(I1) or Pt(II)], and presumably results
from the superior 7T-acid and poorer O"-donor properties of 1,5-COD
compared with arenes when attached to Ir(I).
An important development for future stereochemical and mechanistic
studies is the first synthesis of optically active [Fe(11-Cp*)(11-C6H6)t
complexes, via ligand exchange of benzene with optically active ferrocenyl-
cyclohexanones in the presence of AlCh. (45)
12.2.2.6. Reactions at Side Chains and Exocyclic Carbocations
Kinetic studies have been reported(46) for the addition of water and
for deprotonation in aqueous acetonitrile for the ferrocenyl(Fc)-stabilized
carbo cations 37 (R
1
= Ph, R2 = Ph, CPh
3
, or But; Rl = Fe, R2 = H, Me,
or Ph) (Scheme 5). Both alcohol and alkene products were formed from
Scheme 5
$ R1

Fe
@
37
FcC+(Ph)CH
2
R (R = Ph or But) and Fc
2
C+CH
2
Ph, but FcC+(Ph)CH
2
CPh
3
reacted exclusively by deprotonation, and FC2C+CH2R (R = H or Me)
mainly (>90%) by addition. Bulky {3 substituents (But and CPh
3
) retarded
both addition and proton loss due to steric and conformational effects. A
detailed analysis of ionic strength effects on the various processes was also
undertaken. In an extension of these studies, Bunton and Watts et ai.(47)
have shown that base-catalyzed proton elimination from the I-ferrocenyl
cations 37 (R
1
= Ph, R2 = But; Rl = Fc, R2 = H) with unhindered tertiary
amines follows the Brj1jnsted catalysis relationship in H
2
0/acetonitrile.
Brj1jnsted slopes of 0.32 and 0.45, respectively, were obtained for these
two cations, suggesting that proton transfer is far from complete in the
transition states for elimination. Oxygen bases and sterically hindered
amines were much less effective for deprotonation than unhindered nitrogen
bases of the same basicity. The kinetic {3 -hydrogen isotope effect (kH/ k
o
)
varied between 4.2 for water and 6.7 for pyridine as catalyst. These
observations, together with the effects of added Cl- ions, suggested that
both ion-pairing and initial-state conformation are important in determin-
ing overall reactivity, the Brj1jnsted slopes, and the kH/ko ratio.

[Q(("R
,
Fe ((0)3
38
pKR+ values have been measured(48) for the related carbocations 38
(R\ R2 = H, Me, or Ar), generated from the appropriate alcohols in
trifluoroacetic acid/H
2
0 mixtures. These cations were shown to be
considerably more stable than phenyl-substituted carbocations such as
C
6
H
5
CRIR2 and [Cr(COh(11-C6H5CRICR2)], indicating the strong
ability of the cyclobutadiene iron tricarbonyl system to donate electron
density to an electron-deficient center. However, it is less effective than a
ferrocenyl group.
Deprotonation of the 1T-fluorene ligand in [Cr(COh(11
6
-fluorene)]
using excess KH in THF at 30C has been found(49) to occur ten times
faster than with free fluorene. At this temperature the product is the 11
6
anion 39, although at -20C the isomeric 11
5
species 40 is formed. The
base-catalyzed transesterification of methylbenzoate when coordinated to
Cr( 11-C6H6t also differs from that of the free ester by several orders of
R1

@)-C(O
'
\
\
R Fe
Cr(COI3 Cr(COI3

39 40 41
12.3 Electrophilic Attack
317
magnitude. (50) This confirms the electron-withdrawing character of the
Cr( 71-C6H6t unit.
. Stereoselectivity in the cydization of CJ -lllkyl-P "phenylpropjQnic acids
in polyphosphoric acid to give exo and endo diastereomers of [Cr(COh(71
6
-
indanone)] appears to be under steric control.(51) A method using optically
active complexes has allowed the determination of the kinetic product in
a thermodynamically controlled reaction. In another stereochemical study,
electroreduction of ketones such as 41 (R = Rl = Me; R = Me, Rl = Ph)
has been shown(51) to be regiospecific on the carbonyl substituent rather
than the ring, in contrast to chemical reduction. As illustrated in equation
(20), electroreduction of 42 occurs stereospecifically from the exo side,
giving only the endo alcohol.

I 0
pH= 0
I OH
Fe +
..
Fe +
(20)

E=-10Y

2e- + 2H+
42
12.3. Electrophilic Attack
Hydrogen/deuterium exchange rate constants for the complexes 43
(A = CH
2
, CH
2
CH
2
, CO, 0, or absent) in CF
3
COOD are somewhat lower
than for the corresponding free binuclear arenes. (52) However, replacement
of a CO ligand by PPh
3
causes a marked increase in the nucleophilicity of
the arene rings, the HID exchange rate increasing by 2-3 orders of magni-
tude. For these dicarbonyl(triphenylphosphine) complexes, ring sub-
stituents such as Ph, PhCH
2
, PhCH
2
CH
2
, and PhO have little effect on the
exchange rate (in sharp contrast to the free binuclear arenes) or on the
site of electrophilic attack. Protonation of the carbon atom u-bonded to
chromium(III) in 44 and related cations has been proposed(53) as the first
step in the aquation of these species.
Q-A-Q
43
I
Cr(COI3
44
318
12 Reactivity Qf Coordinated Hydroca,bDHc
Extended Hiickel molecular orbital calculations and uv [He (I) and
He (II)] photoelectron spectral studies on indanylchromium tricarbonyl have
been used to rationalize the regioselectivity of electrophilic attack on the
ring.(54)
12.4. Cycloaddition Reactions
Kinetic studies of the 1,3 cycloadditions of tetracyanoethylene (TCNE)
to tricarbonyl (7J6-cyclohepta-1,3,5-triene) iron 4S (R = H) and related
complexes to give adducts of type 46 have confirmed their concerted
nature.(55) The small rate increases on changing from dichloromethane to
the more polar nitromethane solvent ruled out an ionic intermediate, and
a free radical mechanism had been previously excluded. Comparison with
free cyclohepta-1,3,5-triene showed that coordination to Fe(COh increased
Scheme 6
{fR
k,
fIt.'
7
+ TeNE
>
:-Fe X
"'"'k
X
(CO)3Fe
-1
x
4S
46

Fe-j
the rate by a factor of 740, in keeping with the known electron-withdrawing
nature of the Fe(COh group. In contrast, complex 4S (R = CHO) was
observed to undergo two parallel reactions, in which a rapid but reversible
1,3 addition was in competition with a much slower but irreversible 4,6
addition (Scheme 6). Frontier orbital Hiickel-type calculations(56)
confirmed that 1,3 addition is the preferred cycloaddition mode for TCNE
to a range of cyclic triene complexes.
Chapter 13
Rearrangements,
Intramolecular
Exchanges, and
Isomerizations of
Organometallic
Compounds
13.1. Mononuclear Compounds
13.1.1. Stereochemical Nonrigidity in Metal Carbonyls and
Their Derivatives
In this section we will deal with intramolecular ligand site exchange in
metal carbonyls and their derivatives of a type that does not fit into later
categories such as rotation about a metal-ligand axis, etc. Here we are
mostly concerned with commutation of ligand sites by deformations of
angles between ligands leading to new coordination geometries in inter-
mediates.
In most cases we firstly distinguish intramolecular from intermolecular
exchange. A normal criterion for intramolecular exchange of the type shown
in equation (1) is that it should occur without exchange with any free ligand
cis-[M(CO)4(13CO)P(OMehJ trans-[M(COM
13
CO)P(OMehJ (1)
319
320 13. Rearrangements, Intramolecular Exchanges, arid Isomerizations
present. It was earlier shown that under 13CO (M = W) the reaction occurs
without increase in 13CO content and without formation of [W(CO)6]
expected for CO or P(OMeh dissociation, respectively. In contrast an
intermolecular exchange was established where M = Mo by the observa-
tion of 13C nmr satellites due to 13C_l3C coupling in the product. This
naturally requires more than one 13CO in some of the molecules. (1) The
cis to trans conversion of [Cr(CO)4(
l3
CO)(PPh
3
)] may be carried out
intramolecularly.(2) No 13CO is incorporated when the reaction is carried
out under this gas nor is [Cr(CO)6] formed. The rates of CO dissociation
(3 x 10-
10
S-1 at 30C) and PPh
3
dissociation (9.97 x 10-
5
s-1 at 130C)
may be compared with the cis-trans isomerization rate of 3.13 x 10-
5
S-1
at 40C. Intramolecular cis-trans CO exchange is found for [CrH(COhr
but not the Mo or W analogs.(3) The intimate mechanisms have not been
defined but may involve trigonal prismatic or bicapped tetrahedral inter-
mediates. An interesting feature of the reaction in Scheme 1 is its stereo-
specificity; the trans product is formed by subsequent isomerization. This
requires that the isomerization of the five-coordinate intermediate must
be very rapid. (2)
PPh
3
OC"", I ""CO
'Cr" -
oC"1 'CO
PPh
3
Scheme 1
PPh
3
OC"", I ""CO
"Cr"
OC"'- 'CO
o
C
-
OC"" I ",pPh3 13CO
"Cr'" -
OC"'- ...... CO
o
C
OCII
III
I ,\\"pPh3

13C
o
The octahedral complexes [Cr(COMdiene)] also undergo rapid
intramolecular CO site exchange. For a range of acyclic 1,3 dienes
is in the range 39-47 kJ mol-
1
although the cyclohexa-1,3-diene complex
undergoes much more rapid exchange and the 1,5-cod one shows no nmr
line-broadening up to 345 K. Without any evidence, trigonal bipyramidal
or bicapped tetrahedral intermediates have been considered.(4)
13.1 Mononuclear Compounds 321
Activation parameters in intramolecular CO exchange in
[Fe(COh(diene)] (15 different dienes) 35-60 kJ mol-I) have
been measured and discussed. Substituents at the 1 and 4 positions of the
1,3 diene which lower the LUMO energy increase the exchange barrier
while substituents at the 2 and 3 positions have little effect. Explanations
in terms of Fe-diene bonding are offered.(S) In [Fe(COh(diene)] but not
in [Cr(COMdiene)] the fiuxionality might be regarded as diene rotation.
The complex [FeL
3
(MeN=N-N=NMe)](L = CO) has equivalent Me
groups and very rapid L site exchange, likewise where L = P(OMeh. For
[Fe(CO)Lz(MeN=N-N=NMe)] the Me groups are different and coales-
cence behavior has been studied. Bulkier ligands L give higher exchange
barriers.(6) The intramolecular exchange behavior of [MO(CO)z(1/3 -C
3
Hs)-
(bipy)(CF
3
CO
z
)] (which exists as isomers)(7) and of [V(1/-C
s
H
s
)(CO)-
(PhzPCHzCHzPPhCHzCHzPPhz)] (8) has been described. There has been
an electrochemical study of the kinetics of lac-mer isomerization of
[ReCI(COh(PMezPhht. (9)
13.1.2. Cis-Trans Isomerism and Exchange in Square
Planar Complexes
Certain cis-trans isomerizations of square planar [notably Pd(II) or
Pt(II)] complexes occur spontaneously but most are catalyzed by donor
molecules, which may be free ligands added or generated in solution or co-
ordinating solvents. Two of the mechanisms that have been considered for
the catalyzed reaction are consecutive displacements with four-coordinate
intermediates or intramolecular rearrangements of five-coordinate
transient species. The exchange of methyl groups in 1 is strongly catalyzed
Me
1111, ....
"'Pd'\ :
p'- '0"---
Ph3 Me
1
by added PPh
3
, and to a lesser extent by added py, with kinetic parameters
consistent with an associative pathway. Furthermore the addition of polar
solvents to a chloroform solution leads to an increase of rate proportional
to the concentration of the added solvent. The effectiveness is in the order
HMPA > DMSO > MeOH - MeCN - DMF > MeNO
z
> MezCO, while
THF has no effect. A polytopal rearrangement of a five-coordinate solvent-
coordinated intermediate is proposedYO) Equilibria between four- and
322 13. Rearrangements, Intramolecular Exchanges, and Isomerizations
five-coordinate species have been measured and results discussed in relation
to the mechanism of isomerization of [PtX
2
L
2
] (L = tertiary phosphine). (11)
Others have shown that [PdBr
2
L
3
] is stereo chemically rigid relative to rates
of interconversion of four- and five-coordinate species and use this as
support for a consecutive displacement mechanism. (12)
The MeLi catalysis of the cis-trans isomerization of [PdMe2L2]
(L = tertiary phosphine) is believed to occur via [PdMe3Lr and in support
of this is the Me exchange observed when using LiCD
3
. Autocatalysis in
the spontaneous isomerization of trans -[PdMe2L2] is explained in terms of
a pairwise Me-transfer involving the cis-product [equations (2)_(4)].(13)
Lilli ""Me
LllllllPd"",Me
(2)
IIPd"

+ L
Me; 'L
..
Me;
L 1IIIIIPd "",Me
LIIIII'Pd""",L .. LIIIII'Pd LIIIII'Pd\",\,L
+ +
Me ..... Mel' ...... Mel
..
Me ...... 'Mel Me ........... Mel
(3)
LIIIII'Pd

L 11111'Pd\\\,,\L
(4)
+
L ..
Me ........... Me
l Me; ...... Me
l
Autocatalysis in the spontaneous cis to trans isomerization of [PtIzL2]
(L = PEt
3
or PMe2Ph) is attributed to a liberation of L (the catalyst) in
equilibrium (5) leading to dimer. The addition of [Ir(cod)(phen)t,
which is a known scavenger of L, reduces the reaction rate and increases
h
. d' . d (1415)
t e m uchon peno. .
13.1.3. Stereochemical Nonrigidity in Five-Coordinate
Compounds
(5)
Axial-equatorial exchange in trigonal bipyramidal molecules or
axial-basal exchange in square pyramidal molecules are well known
as facile intramolecular processes. We have already considered the
examples of [Cr(COMPPh
3
)] (Scheme 1),(2) [Fe(COh(diene)],(5) and
[Fe(COh(MeN=N-N=NMe)].(6) Spin correlation between 195Pt and 119Sn
is maintained between -90 to +90C even though axial-equatorial
exchange in the tbp ion [Pt(SnCh)s]3- (X-ray structure) is very rapid. A
classical intramolecular exchange is taking placeY6) Rather more compli-
cated five-coordinate complexes, [PtMe( CHpZ3)]L + (pz = I-pyrazolyl;
L = CO, C
2
H
4
, or various alkynes), are also fluxional with the larger
Scheme 2

energy barriers found for the more electron-withdrawing ligands L.(17) The
substitution shown in Scheme 2 gives specifically the cis rather than the trans
product. Stereochemical reorganization of the five-coordinate intermediate
seems likely. The chelating ligand is ortho-Ph
2
PC
6
H
4
NH
2
YS)
In other cases it is now clear that axial-equatorial exchange in trigonal
bipyramidal molecules is intermolecular. [PdX2(PMe3h] (2) is a par-
ticularly well-studied example. Unlike [NiX2(PMe3h], which requires only
PMC3
X"
'lt
I
"';Pd-PMc
3
X I
PMC3
2
one rate constant to calculate nmr line shapes which match well with the
observed ones, two rate constants are required for Pd. Intra- and inter-
molecular processes operate for Ni and Pd, respectively. Addition of small
amounts of considerably reduces the rate of axial-
equatorial exchange in 2 which is consistent with the involvement of free
PMe3. Compound 2 is stereo chemically rigid relative to the rates of equili-
[PdX
2
L
3
] [PdXL
3
] + x-
L + [PdXL
3
r [PdXL4r
(6)
(7)
bria (6) and (7) (L = PMe3), which lead to the exchangeY2) The complex
3 is important as an intermediate in hydroformylation. The nonequivalent
PPh3 ligands exchange to give coalescence behavior over the temperature

OC" I
""Rh-PPh
OC-' I 3
PPh
3
3
range -80 to - 30C. At higher temperatures an intermolecular exchange
sets in which cannot result simply from reversible PPh
3
dissociation because
at 6C the nmr spectrum shows loss of Rh coupling to both acyl and terminal
l3
C
O nuclei. (19)
13.1.4. Other Examples of Stereochemical Nonrigidity
Nuclear magnetic resonance studies of ligand site exchange in the
octahedral complexes cis-[Ti(IV)(PhCOCHCOMeh(ORh] (R = Pr
i
or
have demonstrated the exchange of the ends of the diketonato
ligands which probably occurs in parallel with inversion of configuration. (20)
The trans to cis isomerization of [MClz(Ph
2
PCH
2
PPh
2
h] (M = Ru or Os)
occurs thermally but may be reversed by direct photolysis into a d-d excited
state. The isomerization is also induced by oxidation since cis - and trans-
[MClz(PPh
2
CH
2
PPh
2
ht readily interconvert; the details of the mechanism
have not been established.(21) A square antiprismatic-dodecahedral inter-
conversion would account for the variation of nmr spectra with temperature
for [U(OEt2h][MPh4(C6H4h] (M = Nb, Ta, or W) but there is no real
evidence for this. (22)
4
The observed nmr line shapes for compound 4 [L = P(OMeh and
M = W] and their changes with temperature are best matched by a pre-
dominant pairwise (13)(24) exchange of ligands L, which correlates with
idealized interconversions of pentagonal bipyramidal, capped octahedral,
and capped trigonal prismatic geometries. In contrast a different permuta-
tional mechanism operates where M = Mo; a nonpairwise (23) exchange
then dominates. (23) The same detail of analysis has not been applied to
compound 5 but it has been shown that Hl_H2 exchange is slower when the
diene is cod than f6f other dienes. (24) Even though the
Me2PCH2CH2PMe2ligand in 6 (Cp' = CsMes) is readily substituted, there
is an intramolecular exchange which occurs faster than an intermolecular
one.(25)
L
H2 I \\\\\\11)
H-'Rc'
HI" "'II
L
s 6
13.1.5. Simple Rotation about Metal-Ligand Axes
Table 13.1 gives some activation parameters for the rotation about
metal-alkylidene bonds in cationic complexes. In some cases the rotation
is too fast for the nmr spectra to be frozen out at reasonably low tem-
peratures; then an upper limit for flG* is given.(28,31) Two isomers of the
CHMe complex of iron would have been generated at -90C but only the
most stable was observed because of rapid rotation. Again an upper limit
for flG * may be set. (27) While in most cases the major origin of the rotational
barrier may be steric, the barriers appear to be modulated by electronic
effects. Larger barriers are found on replacing CO by a tertiary phosphine
and for the more basic phosphines even where these are less bulky. For
Table 13.1. Experimental Barriers for Rotation about Metal-Alkylidene Bonds
Compound flO' kcal mol-
1
Ref.
[FeCp(diphos)(CH
2
)t 10.4 26
[FeCp(CO)(PPh
3
)(CHMe)t <10 27
[WCp(COh(PR
3
)(CH
2
)t
R=Et 9.0 0.1 28
R= Ph 8.3 0.1 28
[MoCp(COh(PR
3
)(CH
z
)t <6.7 28
[ReCp(NO)(PPh
3
)(CH
2
)t >15 29
[ReCp(NO)(PPh
3
)(CHPh)t 20.9 O.4
a
30
[FeCp(CO)(PPh
3
)(C=CMez)t <8.6 31
[FeCp(CO)(PBu3)Lt
L = cycIoheptatrienylidene 9.6 0.2 32
L = 4,5-benzocycIoheptatrienylidene 10.4 0.2 32
a IlH*; IlS* = -3.8 0.2 cal K-
t
mol-to
l11i 1 J Rearrangements, Intramolecular Exchanges, and Isomerizations
example, a higher barrier is found for the tungsten PEh complex than for
the PPh
3
one. In the latter there would be less metal 7T donation to the
alkylidene carbon atom. (28) Similarly the cycloheptatrienylidene complex
gives a lower barrier than the 4,5-benzo-derivative even though the steric
crowding at the metal is identical. Benzannelation should increase 7T dona-
tion from the metal atoms. The rhenium compounds in Table 13.1 have
particularly large barriers and some interesting photochemical effects have
been observed for them. (30) Photolysis of the thermodynamically stable
isomer (7b )(>99%) at -22 to -78C gave an approximately equal mixture
of the two isomers (7a) and (7b). Thermal relaxation back to the thermody-
namic mixture, that is mainly isomer (7b), has been followed kinetically
[t1/2 at 4C = 443 min for the conversion of (7a) to (7b)],(30) In a theoretical
treatment of [Ni(COh(CH
2
)] a very low barrier of -0.2 kcal mol-I has
been calculated for the sixfold rotation barrier.(33) Clearly rotation barriers
for metal-alkylidene bonds vary enormously.
7a 7b
A few further studies have been added to the many previous ones on
71
2
-alkene and 71
2
-alkyne rotation. While extended Hiickel calculations on
Zeise's salt had given the correct ethene orientation, the calculated rotation
barrier, even allowing for geometric relaxation of the PtCh unit, was
much too large. A more recent ab initio treatment has given a value of
15 kcal mol-
1
for the barrier in [PtCh(C
2
H
4
)]- close to the experimental
value in similar molecules and higher than that calculated for palladium
(7 kcalmol-
1
).(34) The barrier seems to be largely steric (as expected for
a class S rather than class T type of alkene complex(3S)). Rotation barriers
have been determined experimentally for [W(C
s
H
s
)Me(COh(C
4
H
4
)] using
partially deuterated ethane) and its indenyl analog,(36) in
[Co(CsHs)Me2(C2H4)],(37) and in [Mo(EtC_CEt)z(S2CNMe2)z].(38)
With 71
3
-allyl complexes the two major types of fiuxionality operating
are allyl rotation about the M -allyl axis and 71
3
-71
1
-71
3
interconversion.
The 71
3
-71
1
-71
3
path is characterized by an associated exchange of the syn
and anti substituents at the allyl terminus, while for allyl rotation this
exchange cannot take place. The complexes [M
2
(allyl)4] (M = Cr or Mo)
have two bridging and two terminal 71
3
-allyl ligands with the minor (8) and
major (9) configurations both present in solution. Their rates of interconver-
13.1

Mononuclear Compounds 327
>0<
./"'-....
/'..

8 9
sion are too slow for nmr coalescence but above 30C (Cr) or above
80C (Mo) magnetization transfer studies have established that the isomers
interconvert without syn-anti exchange at the terminal allyl ligands. The
syn protons of the terminal allyl of 8 exchange with the syn ones of 9 and
likewise anti with anti. A terminal allyl ligand rotation is required.
Another process observed for Cr but not Mo is a rotation of the IL -allyl
ligands to interconvert 9 and 10 and again a '111 -allyl cannot be involved. (39)
./"'-....
/'..

10
[M(allyl)4], however, shows fluxional behavior above 70C (M = Mo)
or above 90C (M = W) with both syn-anti exchange and syn-syn (anti-
anti) exchange which can be identified separately by magnetization transfer
as the nonequivalent ends of the '11
3
-allyl exchange. (39) 'I11-Allyl species are
involved as intermediates.
In CD3N02 at 100C the exo and endo (syn, syn) isomers 11 and 12
rapidly interconvert without involvement of isomer 13, which gives separate
Q
+
Q
+
Q
+
Mn
oc'''':'l
n
,:",,,co
Mn
OC"'''' I """CO
oO'po
'0iV

..-v",
11 12 13
nmr signals even after coalescence of signals due to 11 and 12. Allyl rotation
is faster than an '11
3
_'11
1
_'11
3
process. (40) Exo-endo interconversion for
[Ru(CsHs)(CO)(allyl)] is so slow in contrast that isomers may be separated
by fractional crystallization. The kinetics of the conversion of the endo to
exo isomer (>98% at equilibrium) have been measured: k =
(5.60 0.08) x 10-
4
S-I, at 119.5C. Rotation barriers [dO* 28.9 0.6
(allyl) and 31.4 1.6 (2-methallyl) kcal mol-I] are both higher than for
iron [LlG
t
- 24 kcal mol-
1
]. Attempts to define the mechanism by mag-
netization transfer methods were not possible so that although a 1} 3 -1} 1_1} 3
mechanism is preferred it has not been established.(41)
Exo-endo interconversions in [Mo(CsHs)(NO)I(1}3-allyl)] occur by an
1} 3 -1} 1_1} 3 mechanism while allyl rotation is faster for [Mo(CsHs)-
(COh( 1} 3 -allyl)] and [Mo(C
s
H
s
)(NO)(CO)(1} 3 -allyl)t. Resolution of the
enantiomers of the the iodide where allyl = cycloctenyl has been achieved
spontaneously by crystallization. The endo-exo interconversion of the (R)
isomer shown in Scheme 3 could occur by clockwise or anti clockwise
Scheme 3
..
"""
IICO
rotation. Since the isomerization has the same rate as for the C3HS complex
and is faster than the 2-methallyl complex, a clockwise rotation is preferred.
A rotation in this direction brings the 2-position of the allyl close to the
Cp ligand and hence is slowest for the 2-methallyl compound. (42)
The calculation of rotational barriers for trimethylenemethane and
cyclic polyene complexes has been reviewed. (43) Several experimental
studies of ring-whizzing of cyclic polyenes have also been reported. The
two C
s
rings in 1,l',4,4'-tetra-Bu
t
-uranocene are oriented with respect to
each other such that the six protons of each ring are nonequivalent and
give six lH nmr signals at -lOOC. Rotation of the rings (LlG
t
=
8.3 kcal mol-
1
) leads to pairwise coalescence giving three signals at 70C.
A much higher barrier (13.1 kcal mol-
1
) is found for the 1,l',3,3'-tetrasub-
stituted isomer. (44) Bulky substituents at rings normally increase rotation
barriers and rigid conformers are present up to lOOC for [Co(1}s-1,3-
and its oxidation product [Co(1}s
(PMe3hRt (R = H or Me). Slightly reducing the bulk by replacing one
But by a Pr
i
group results in the need for temperatures below -lOoC to
freeze out conformers. (4S) Restricted rotation is found with [Ru( 1} s -
C
6
H
6
PR
3
)L
3
f+ (L = tertiary phosphine).(46) Inelastic neutron scattering
studies have given the rotation barriers for [Cr(C6H6 )(COh], 27.5;
13.1 Mononuclear Compounds
[Mn(C
6
H
6
)(COh]Br,
15.5 kJ mol-
1
.(47)
46.5;
329
12.6;
The crystal structures of various Ni, Pd, and Pt triphenylcyclo-
propenium complexes of type [M(C
3
Ph
3
)(PPh
3
ht have been determined.
While the Pt complex with PF6" as counterion adopts structure 14, the Pd
cation with PF6" and ClO;; have structures 15 and 16, respectively, and the
Ni complex adopts structure 17. An analysis of the details of these solid
state structures in conjunction with MO calculations has led to the con-
clusion that these chart out the likely pathway for ring-whizzing as shown
in Scheme 4. (48)
Scheme 4
0
0
0
\ /1""-
'/1"

l'Y-
O
M I/C
- M--C
M-C
-

1
1
/ o fi/
I'c
o C
0
0
14 15 16 17
13.1.6. Ligand Motion Requiring Changes in Hapticity
In the previous section we have already considered some examples of
the 1/ 3_1/ 1-1/ 3 mechanism as an alternative to allyl rotation. This is a special
case of a mechanism involving a change in hapticity which necessitates
the interconversion of saturated and unsaturated species. [Hf(CsMes)-
(1/ 3 -C4 H7)( 1/ 4 -C4H6)] provides another example in which the same process
that leads to syn-anti exchange at the allyl also exchanges the ends of the
1/ 4 -butadiene. (49) 1/ l-Allyls might also be expected to be fluxional if 1/ 3 -allyls
are accessible, but coordinative saturation is an important consideration.
Even so there is evidence that the ends of the allyl in [Fe(CsHs)-
(COh(1/ I-allyl)] can interchange. Studies on the more stable [Fe(CsHs)-
(CO)L(1/ I-allyl)], where L = P(OCH
2
hCMe, have ruled out an
intramolecular mechanism for the 1,3 shift at the allyl. Crossover experi-
ments support a radical chain mechanism with the chain-carrying radical
[Fe(CsHs)(CO)L] attacking an 1/ I_allyl by an SH2' process. Allyl ligand
transfer between Fe atoms thus occurs.(SO)
Allyl transfer has also been for the exchange of the two
allyl ligands in the salt [Pd(1/ -1-methallyl)(TMEDA)t[PdCh(1/3-1-
methallyl)r which is accompanied by syn-anti hydrogen exchange. A
dinuclear intermediate with bridging allyl ligands has been proposed. (51)
In these cases we can see that intermolecular processes can account for
observations like syn-anti -substituent exchange normally discussed 10
intramolecular terms.
As with 1/ 3 -allyls, 1/ 4 -dienes may undergo two basic types of
intramolecular process: diene rotation and a flipping mechanism in which
the system passes through a l,4-di-a-form (i.e., a metallocyclopentene)
which is unsaturated with respect to the parent molecule. This ability to
flip (Scheme 5) seems to be a particular property of the earlier transition

I
M
Scheme 5
Q
$
..
$
..
M
:;J
I
M
metal 1/ 4 -diene complexes. The process has been identified for [Hf(cot)-
(1/ 4 -C
4
H
6
)] by the coalescence of the terminal proton nmr signals of the
butadiene. With the Zr analog the exchange is much slower but nevertheless
demonstrated by magnetization transfer. (52) Likewise flipping has been
found for [W(C
4
H
6
h] but not [Mo(C
4
H
6
h]' (53) The coalescence tem-
perature for flipping in [HfCp2(C
4
H
6
)] is much lower than for
[ZrCp2(C
4
H
6
)].(S3) The metallocyclopentene form would appear generally
more accessible energetically for third-row metal than second row; its
formation is formally at least an oxidation. No coalescence is observed for
[W(o -C
6
H
4
(CH
2
hh], which gives a temperature-invariant AB quartet (CH
2
protons) in the IH nmr spectrum, even though the complex is related to
[M(dieneh] and might be expected to have a more accessible di-a-bonded
form.(S4)
13.1. 7. Metal Migration between Different Ligand Sites
Studies on [Fe(C
s
H
s
)(CO)L(1/ l-CsH4R)] (R = H or Me) where L =
PF2NMe2 have shown that the well-known migration of Fe about the
1/ 1 -cyclopentadienyl ligand occurs with retention of configuration at iron
since the diastereotopic F atoms do not exchange. Furthermore, since the
ring protons of the 1/ l-CsH4Me ligand give an ABCD IH nmr spectrum
even at the fast exchange limit the asymmetric Fe atom must remain at
one face of the ring. A suprafacial migration with retention at iron is
13.1 Mononuclear Compounds
331
confirmed which is, of course, consistent with commonly accepted ideas. (55)
Spin saturation transfer studies on the 1/ I-tropylium complex [Ru(C5Hs)-
(COh(1/ 1-C
7
H7)] have given the rate constants (1.7 0.4) x 10-
2
S-1 for a
1,2 shift, (O.lO.l)x 1O-
2
s-
1
for a 1,3 shift, and (0.30.1)x 1O-
2
s-
1
for a 1,4 shift. Thus a 1,2-shift mechanism predominates with a minor (and
probably significant) contribution from the l,4-shift mechanism.(S6)
The 173-benzyl complex [Rh{P(OPrihh( 173-CH2C6Me5)] (X-ray
structure) undergoes the rapid exchange (A) (Scheme 6) since the two
ortho-methyl groups are equivalent in the nmr spectrum between -75 and
Scheme 6
(AI
+80
a
C. Since the P nuclei remain nonequivalent up to 80
a
C this cannot
involve a 14e 1/ I-benzyl intermediate but a suprafacial shift as indicated.
To explain the very large changes of chemical shift in the 31p{IH} nmr
spectrum but no coalescence, it is proposed that there is a rapid exchange
between two isomers the proportions of which vary with temperature. The
16e and 18e molecules related by equilibrium (B) have been proposed.(57)
Ring-whizzing of a 1/
2
-cyclooctatetraene compound [Ta(C5H5)z(nPr)-
(172-CsHs)) has been described.(5S) A detailed analysis of the 1,3-iron shifts
in [Fe(COh(1/4-cycloheptatriene)) and related species has supported an
1/ 2 -cycloheptatriene intermediate. Calculations, however, suggest that the
16e intermediate implied in Scheme 7 is stabilized by a movement of iron
Scheme 7
o
I
Fc(COI
3
toward the center of the ring but not so far that the molecule approaches
a 20e-1/ 6 description. A noncaradiene-type intermediate is ruled out. (59)
Constants for the equilibrium between isomers 18 and 19 as well as
kinetic data for their interconversion have been reported. (60)

18 19
Some iron(61) and ruthenium(62) complexes containing bidentate BH4"
ligands are fluxional. For example, compound 20 undergoes two distinct
20
intramolecular processes, the faster of which involves exchange of H
a
with
Hb but not H
C
This apparently results from a cleavage of the the Ru-Ha
bond, rotation about Ru-Hc and B-Hc, and rechelation. A slower process
exchanging all four BHi hydrogen atoms may be similar but involving
Ru-Hc cleavage. (62)
Several pUblications have reported fluxional behavior involving a
potentially bidentate ligand bound through just one heteroatom.
Intramolecular exchange of a metal-bound and a free heteroatom is
reported for [Pt( 1/ 2 -S2CNEh)( 1/ 1 -S2CNEh)(PPh
3
)](63) [Pt( 1/ 1 -Ph
2
PCH
2
-
PPh
2
h(C=CRh],(64) [PtCl(1/ l-ArN-N=NAr)(PPh
3
h](65) [M(CO)s-
(1/1-Me3SiCH2S2CH2SiMe3)] (M=Cr, Mo, or W),(66) and [Pd(Me2NCH2-
C
6
H
4
)X(1/1_RN=CHCH=NR)].(67) In all cases coalescence behavior is
observed; all the Pt compounds might be expected to exchange by an
associative route.
13.1.8. Migrations and Interchanges Involving Hydrogen Atoms
There has been a very interesting case reported where the reversible
insertion of ethylene into a metal-hydrogen bond is faster at one end of
the alkene than the other. Protonation of [Co(1/-C5Me4Et)(C2H4h] gives
21
the cationic form 21.(68) Reversible hydrogen atom transfer involving an
ethyl intermediate was established by isotopic labeling and spin-saturation
transfer. Exchange of hydrogen e with c and d (Ea 30 kJ mol-I) is more
rapid than with a and b (Ea 40 kJ mol-I). Clearly the barrier to alkene
rotation differentiates the ends of the alkene. Spin-spin coupling is observed
between hydrogens e, c, and d, which might result from the orbital overlap
required to lead through to the ethyl intermediate.(68)
Following reports on Fe-H-C bonding in [Fe(P(OMehh(1]
3
-cyclooc-
tenyl)t, several more very similar examples have been reported since 1981
involving manganese(II), (69-71) ruthenium(II), (72) or iridium(III), (73) all of
which are d
6
five-coordinate species 22, unsaturated were it not for the
22
hydrogen bridge. Protonation of [Mn(COh(1] 4 -cyclohexadiene)r gives the
compound [Mn(COh(1]
3
-cyclohexenyl)], the X-ray structure of which sup-
ports earlier nmr evidence for a strong nontrivial Mn-H-C interaction
[Mn-H 1.86(2) A] involving a CH
2
group adjacent to the 1]3 -allyl. In spite
of the robustness of this system the complex is fluxional with three distinct
processes. There is an oscillation with the endo C-H bonds on either side
of the allyl interchanging, each being involved successively in the Mn-H-C
bridge (1l0* 8.3 kcal mol-I). There is a slower exchange of the CO ligands
(1l0* 13.1 kcal mol-I) which probably involves dechelation of the coordin-
ated CH followed by allyl rotation in a 16e intermediate. The slowest
process identified (1l0* 15.4 kcal mol-I) exchanges all ring carbon atoms
probably as in Scheme 8 which, in conjunction with the fastest process
6
5
Scheme 8
I 6
20
5
31 '4
(COl
3
MnH
H I 6

M{3-\J
(COb 3 '4
above, allows the manganese atom to progress around the six-membered
(69-71)
nng.
Observations related to this have been made on compound 23. The
fastest process (H1_H2_H3 exchange) has not been frozen out although the
Me
6
r
5
Me*C-H'4
: (-;RU(dPpeHPMC
2
Phl
Mel
Me'
23
averaged signal (8 -2.31) starts to broaden at -90C. Between -30C and
+80C the diastereotopic PMe signals collapse as Me
7
exchanges with Me
9
and Me
6
with CH1H2H3; an 1/3_1/1_1/3 process would account for this but
the mechanism may be the same as for the Rh case in Scheme 6 above.
Above 28C it seems that total exchange of the hydrogen atoms on the
hydrocarbon ligand occurs possibly via an ortho-xylylene hydrido inter-
mediate. (72) The iridium compound 24 shows very similar behavior:
exchange at the Ir-bound Me group with a slower exchange via
[IrH
2
(diene )(PPh
3
ht. (73)
+
24
The tautomers in Scheme 9 (L = PMe3) are in equilibrium in solution
but give separate 1H nmr signals. Spin-saturation transfer experiments at
Scheme 9
L L
CL", I ""II
"ra"
MC3CICH;'""" I 'CI
L
CI", I ",Et
H "ra"
I 'CI
MC3C2 L
25 26
- 30C have shown that magnetization may be transferred from C
1
to C
2
or in the reverse direction. There is an extra complication in that the
nonequivalent ligands L in 26 exchange faster than the tautomeric equi-
librium. Specific M-H-C interactions at the Et or CHCMe3 ligands have
been invoked to account for features of the nmr spectra and the non-
equivalence of L.(74) Rapidly interconverting tautomers shown in equation
(8) have also been studied (dmpe = Me2PCH2CH2PMe2) and in this case
[Ta(CCMe3)H1(dmpe)zX] [Ta(CH2CMe3)(dmpe)zX] (8)
coalescence has been observed. Signals due to HI (8 2.30) and H2 (8 -9.7)
observed at -68C coalesce to a quintet (8 -3.20) at 50C. Since the
isomers are approximately equally abundant, the averaged signal is correctly
positioned. (75)
There have been conflicting reports of a - and {3 -elimination in the
conversion of platinacyclobutanes into alkenes but some definitive evidence
has now proved that a elimination is dominant. Scheme 10 shows how
isotopic labeling has been used; no CD
2
=CMeCH
2
CH
3
expected for
{3 -elimination is formed. (76)
Scheme 10
L
-
(py)
CI
I CDH
L-pt-II
I C
CI / \
CDH
II
/c""
Mc CHDMc
4
Me CHDMc
13.1.9. Intraligand Rotations and Rearrangements
Certain effects observed in nmr spectra relate to the interconversion
of equivalent or different conformations of chelate rings. For example, the
low-temperature 3l
p
nmr spectrum of (-)-[Pd(diop)z], where diop is the
well-known diphosphine 27, shows an AA'BB' spectrum which coalesces
27
at higher temperatures = 41.2 kJ mol-l). Interchange of conforma-
tions in the seven-membered rings is believed to be the cause.(77) Tem-
perature-dependent exchange effects have also been observed for the
chelate ring 28 (78) and for 29.(79) For example, 195Pt nmr studies on
Q
5-5
/ \
M CH
2
M 5
0
\ /
s-s
28 29
[Pt(S5h]2- show two nonequivalent forms which interconvert =
50.5 1.3 kJ mol-l).
30
The four-membered rings in compounds 30 (R = C0
2
Me) are not
planar and Table 13.2 gives angles () determined by X-ray diffraction. The
energy barriers to ring inversion determined by nmr methods decrease with
decreasing (). (80)
Ring inversion has also been studied for the [3]ferrocenophanes
where the two cyclopentadienyl rings are linked by the chains
13.2 Dinuclear Compounds
Table 13.2. Barriers to Ring Folding in Compounds
30 (R = C0
2
Me/
80
)
Compound
();o
4afc/kJ mol-
1
30; L = PPh
3 54.0 50.9
30; L = AsPh
3 52.7 44.4
30; L2 = bipy 51.3 40.4
337
(81) ( ) (82) d
-CH
2
CH
2
CH
2
- or -XXX- X = S, Se, or Te . Pyraml allOver-
sion at Sand Se and other intramolecular exchange behavior has been
studied for a series of thio- and seleno-ether complexes of rhenium, (83)
platinum, (84-86) and palladium. (86)
13.2. Dinuclear Compounds
13.2.1. Migration of Carbonyl Ligands
Pairwise exchange of two CO ligands as in Scheme 11 is well known.
The normal (lowest-energy) form may have either terminal or bridging CO
o
c
I
M--M
I
C
o
Scheme 11
-
-
-
-
ligands or may be anywhere in between these two extremes. An example
of oscillation of two asymmetric CO bridges via a symmetrically bridged
form so as to generate a time-averaged plane of symmetry is provided by
[M02(CsHsh(COh(11-diene)].(87) A process as in Scheme 11 also accounts
for the facile merry-go-round behavior of the six equatorial ligands in 31,
which contains the diphosphine Ph
2
PCH
2
PPh
2
(dppm).(88) This contrasts
with the stereochemical rigidity of [Mn2(COho] which unlike 31 is stag-
gered. At least [Mn2(COho] is staggered in its low-pressure crystalline form

o PoP
C, I c" I
',1. '"
OC-Mn--Mn-CO
I'c I'c
pOp 0
'-...../
31
but eclipsed after a solid state phase transition at high pressures. (89) The
different behavior between [Mn2(COho] and 31 may result from conforma-
tional differences although in solution there is a very low rotation barrier
for [Mn2(COho].
The interesting pentacarbonyl derivative of 31, [Mn2(CO)s(dppmh],
undergoes the process in Scheme 12. Variable-temperature 13C{31
p
} nmr
Scheme 12

o 3 I I 40
e'l/II \\\\,C
"Mn--Mn"
c
2
",- I 'el/'I ""c
s
o 0

-
-
shows pairwise collapse of signals for carbonyls 1 and 3 and for carbonyls
4 and 5, while the signal due to 2 remains sharp. The Mn atoms remain
distinguishable. An unsaturated intermediate may be involved but more
likely there is a concerted interchange of C
1
and C
3
.(88)
The interchange of the terminal with the semibridged CO ligands in
32 occurs more rapidly than the exchange of the 31
p
nuclei = 12
1 kcal mol-I). The latter is believed to require bridge-terminal exchange
involving both CS and CO.(90)
32 33
13.2 Dinuclear Compounds 339
Compound 33 gives five 13CO nmr signals (1: 2: 2: 1: 1) at -132C
consistent with there being three symmetrical CO bridges as in [Fe2(CO)9]
and not as found in the crystal (see structure illustrated). There is either
a change in structure in solution or structure 33 persists but undergoes a
rapid oscillatory motion. The most simply envisaged processes at higher
temperatures to fit the data are a combination of a conversion to a mono-
bridged structure (like that of [OS2(CO)9]) and axial-equatorial exchange
of the Berry type at the un substituted Fe (fast) and at the substituted Fe
(slower). All CO ligands exchange rapidly at 110C. (91)
Local CO exchange at the two metal atoms in [Fe2(CO)6-
(/J- -ButNCHCHNBu
t
)] occurs at different rates and similar behaviorisfound
in the heteronuclear complex where the metal atoms are manganese and
cobalt. (92)
13.2.2. Hydrogen Migration Reactions
Bridging and terminal hydrides may exchange (as do carbonyl ligands)
and very specific motions may be required to describe nmr coalescence
behavior. The unusual asymmetric molecule 34 [L = PMe
2
Ph; L' =
P(OCH
2
hCEt] has four nonequivalent hydride ligands with four 1H nmr
L'
\ H L
Lilli ' / ........ /. L
1111 Rc--Rc """"
H"\\', 'L'
L H
34
signals at -48C. Intramolecular exchange at higher temperatures of the
two ReL
2
L' units curiously does not generate a time-averaged mirror plane
through the Re atoms (that is, the PMe2Ph groups remain diastereotopic). (93)
The compound [Ta2Cl4(PMe3M/J--Hh], 3S (C
2
symmetry), is the parent of
a range of dinuclear hydrides. Its 1H nmr spectrum is only consistent with
3S
a rapid rotation of the two [TaCh(PMe3hJ groups with respect to each
other. The IL -hydride motions must be linked with this rotation. (94)
Rather more important is the migration of hydrogen atoms between
carbon and metal atoms. The equilibrium in Scheme 13 is slow with the
H
/
Cp2Nb=C H
I \ I I
H O-ZrCp2
Scheme 13
-
-
complex existing almost totally as the IL -formyl tautomer with separate
NbH and CHO nmr signals. However, by introducing D at the formyl
group exchange between NbH and CDO was observed at -80C and by
applying spin-saturation techniques the rate was shown to be concentration
independent and the reaction is probably unimolecular. The unsaturated
IL -CHzO tautomer shown is trapped by CO about 4000 times slower than
the a -hydrogen elimination to regenerate the IL -CHO tautomer. Studies
of rapid tautomerizations of this sort are an important recent
development. (95)
Related to hydrogen transfer between carbon and metal is the behavior
of IL -CH3 compounds such as [FezCpz(1L -CO)(dppm)(CH3)t 36 (X-ray
+
36
structure/
96
) and [Fe
z
Cpz(IL-CO)(CO)z(CH
3
)t.(97) The three hydrogen
atoms of the methyl group, including that in the Fe-H-C bridge, are in
rapid exchange. The 8CH nmr) value -2 ppm is an average of two low-field
and one high-field signals. The CH
3
, CHzD, and CHD
2
compounds give
very different chemical shifts (temperature dependent for CHzD and CD
2
H)
because of the large equilibrium isotope effect. Rates of intramolecular
exchange are too rapid to freeze out nmr spectra.
13.2 Dinuclear Compounds 341
13.2.3. Motion Involving Bridging Organic Ligands
The related complexes _CH
2
)](97) and
both exist as a cis-trans mixture in
solutions, isomers 37 and 38. For the tetracarbonyl analogs [M
2
Cp2(CO)4]
R R R R

Oc 0 oc
IIIIIII'M/ "M\\\\\\\\C """"M/ "M\\\\\\\CP
Cp........ 'c/ "'Cp Cp........ "'c/ "'co
o 0
37 38
these isomers rapidly interconvert (nmr coalescence) but the isomers of
[Fe2Cp2(COh(CH2)] have been physically separated (t1/2 at 25C for cis
to trans isomerization is 10 min). The isomerization is more rapid for the
CMe2-Ru2 complex (dO* around 20 kcal mol-I) but still very much slower
than for the tetracarbonyl. The isomerization must pass through a relatively
unstable terminal CR
2
form to allow rotation about the M-M bond.
Other types of intramolecular bridging ligand motion to have been
studied are the rotation of the 1/3, 1/3 -tropone in [Rh
2
Cp2(tropone)], 39,(99)
the commutation of the two Pt atoms between the three S atoms in 40, (100)
o
CpRh--RhCp
39
and the motions of the eight-membered ring in [Me2Pt(1/-
PH2PCH2PPh2hPtMe2]. (101) In the latter case the PtMe and the 31 P groups
exchange by conformational changes in the twisted saddle ring (Scheme 14).
Scheme 14
*
'P 7
MeG Pt P
Me
b
MeG
Me
b

(*P-"'p
P Pt Me
b
Me
b
MeG
MeG
-
The CH
z
protons exchange more slowly by a saddle inversion. A new and
important observation relates to the rigidity of molecules such as 41. The
Ph C0
2
i
pr
\-c
i

CpNi--Co(CO)3
41
asymmetric MM'CC' framework results in the CHMez groups being
diastereotopic and hence giving two IH nmr doublets. These groups
exchange (aG
t
20.5 0.5 kcal mol-I), presumably by an intramolecular
process because alkyne exchange is much slower. A tetrahedral-square-
planar interconversion is most easily envisaged but Co-Ni cleavage to give
a butterfly which folds over its wings to reform the Co-Ni bond on the
other side is an intriguing possibility that has also been considered. (102)
13.3. Cluster Compounds
13.3.1. Migration of Carbonyl Ligands
The structures of cluster carbonyls have been considered in terms of
a metal skeleton within a sheath of tightly packed CO ligands which define
a closed polyhedron minimizing atom-atom repulsions. A recent account
of this approach has emphasized that intramolecular exchanges require
concerted motion involving all the CO ligands. Even where only some of
the CO ligands apparently migrate, these must squeeze by those that are
immobile so that energy barriers to exchange contain important steric
contributionsy03) [Fe3(CO)d has long presented the interesting problem
of its phase-dependent structure and dynamic behavior. The carbonyl
polyhedron in the solid state is a somewhat distorted icosahedron but there
is disorder in the crystal since the Fe3 unit may adopt orientation 42 or
43. Solid state 13C nmr (magic angle spinning) gives six equal intensity
signals with none assignable to /J-z-CO even though such are present. The
spectrum is interpreted in terms of a rapid interchange of the two orienta-
tions 42 and 43 in the crystal. (104)
42 43
13.3 Cluster Compounds 343
In solutions we need to distinguish intra- from inter-molecular and also
intra- from inter-nuclear CO exchange in clusters. These various reaction
types may easily be distinguished if J(M-
13
C) can be observed.(105,106) The
axial-equatorial CO site exchange known for [Os3(COh2] could result from
exchange localized at each Os (perhaps by a turnstile mechanism) or from
CO migration around the whole cluster. The 13C nmr spectrum of
[OS3(CO)12] (99.8% 1870S, 60% 13C, each I gives two doublets
(J MC = 90 and 115 Hz) coalescing to a 1: 3 : 3 : 1 quartet (J MC = 34 Hz).
Clearly the exchange is intramolecular and internuclearyo5) Similarly the
observation of 57Fe_13C coupling has been applied to the dynamic behavior
of di- and trinuclear iron compoundsyo6)
There is intranuclear (localized) exchange of axial and equatorial CO
in [RU3(COMC=CBu')r, 44, with slower exchange at Ru
1
. The main effect
R
/
<t c:=:Sc CO

c c
00 00
C
o
44
of protonation across Ru
2
-Ru
3
is to greatly reduce the rate of exchange
at these atoms; exchange at Ru
l
is then the faster. This could be a charge
effect but, since there is an HID kinetic isotope effect, the hydride bridge
seems to be disrupted to allow axial-equatorial exchange at Ru
2
and
Ru
3
.(l07)
Cp
C
c ... \ ... c
o
CO
p I Mo \
'\ /
MO---fN-Mo
/ c \
c 0 cp
o
4S
The three cyclopentadienyl ligands in 4S are different but the rapid
exchange of those at the end positions results from exchange of the terminal
and semi-bridging CO ligands. (l08) There is also exchange between bridging
and terminal CO ligands in [OS3(CO)l1f- but the mechanism has not been
defined. (l09)
46
Carbonylation of [RhdCOho]2- gives [Rhs(COhsr, 46, the 13C nmr
spectrum of which under CO pressure is reported. The solution structure
is rather different from that in the crystal; the equatorial-equatorial edges
are symmetrically bridged by CO while the other edges (--it--)
accommodate semibridging CO. No intermolecular exchange with free
CO occurs on the nmr time scale while intramolecular scrambling of
all but the three symmetrically bridging CO ligands occurs. (110)
[Rh
6
(COho{P(OPhh}4] on the other hand gives a 13C nmr spectrum up
to 60C consistent with the crystal structure, but above 60C there is a
reversible process leading to structural changesYll) The carbido-anion
[Rh6(CO)13C]2-, 47, has the structure shown with /-L2-CO along the thick
o
C
I
0c A

/.E-...
Co
"il'c
o
I
C
o
47
Rh-Rh edges. There is a rapid transfer of a terminal CO to a /-L2 position,
while a /-L2-CO becomes terminal (see arrows). This gives time-averaged
triplet, quintet, and doublet 13C signals in ratio 4: 7: 2. The process does
not allow the /-L2 and terminal ligands at the axial Rh atoms A to exchange
but the seven ligands in the equatorial plane of atoms E (five terminal,
and two /-L2) undergo a merry-go-round process around atoms E. Hence
the observed quintet. The process is rapid at -960C. (112)
The 93Nb nmr spectrum of [Nb
3
(C
s
H
s
h(COh], containing an unusual
6e-donating 1L3-CO, is consistent with the migration of this CO between
the Nb atoms as deduced from earlier resultsY
13
)
13.3.2. Hydrogen Migration Reactions
The observation of weak satellites of osmium hydride IH nmr signals
resulting from 1870S_1H coupling (1870S; 1.62%; I = !) has been applied
to hydride migration reactions. The equivalent hydrides in [H
4
0S
4
(CO)d
lie along four of the six Os-Os edges of the tetrahedron with each Os
associated with two hydrides. At -105C J(OsH) = 30.5 Hz, but at room
temperature the hydrides are migr.ating rapidly over all six edges and so
spend half the time associated with each Os atom; the time-averaged
J(OsH) value is then 14.4 HZ.(114) "Hidden" processes may therefore be
studied. Exchange of bridging and terminal ligands H
a
and Hb in
[H
2
0S
3
(COhoL] (L = tertiary phosphine) is associated with CO
exchanges, of CO
A
with COB in particular, and the oscillatory mechanism
in Scheme 15 fits the observations. Coupling of hydride with carbonyl
motions may be important in other cases as wellY
1S
)
Scheme 15
..
r-A ' .... ,1'" I
"","
, I-""'--'H
o
/ I "L
Hb--",
Hydride migration between the two Pt-Rh edges in [PtRh
2
(1L -H)-
(COh(PPh
3
)(C
s
Mesht has been described(116) and between an Os-Os
and a Pt-Os edge in [OS3Pt(IL-Hh(CH2)(COho(PCY3)].(117) Hydride
migrations in [H
2
0S
2
CO(COho(CsH
s
)] lead to coalescence of the two
IH nmr hydride signals.(118)
13.3.3. Motion Involving Bridging Organic Ligands
The motion of 1L3-alkyne and 1L3-aryne ligands in trimetallic clusters
has been observed and discussed in several papers.(1l9-12S) Use of
diastereotopic substituents (-PMe
2
Ph,(119) -CH
2
CH
3
,(120) -CHMe2(122))
at the organic ligands has confirmed that their rotation (Scheme 16) requires
Scheme 16
-
-
the ligand to flip as it rotates so that its opposite faces are successively
involved in 1/ 2 bonding. The RCCR plane is perpendicular to the M3 plane
at some stage of the rotation.
48
For the chiral cluster [FeNi
2
(C
s
H
s
h(COh (PhC == 48, there
is a dynamic process leading to the exchange of the Cp ligands (AG
t
15.1 0.5 kcal mol-I) and presumably two successive rotations like that
in Scheme 16 are required for this. The rotation is slower when a CO at
Fe is replaced by PPh
3
. Where three different metal atoms are involved as
in [FeCoNi(C
s
H
s
)(COMPhC=CC0
2
Pr
i
)] there is no loss of chirality
on rotation. Thus fast interconversion of the diastereomers by alkyne
rotation leaves the CHMe2 groups diastereotopic and so the ligand must
remain above the same FeCoNi face throughout.(126) In [FeC0
2
(COMCEt)]
intranuclear (local) CO scrambling occurs faster at Fe than at Co while an
even slower process involves internuclear exchange (possibly involving
alkyne rotation).o2S) Two isomers of [W
2
0s(CsHsh(COh(ArC-CAr)], 49
Ar
\ Ar

/ "
Cp(CO)2
W
" i>S(COh
W
Cp(COI
2
49 so
and SO, are very interestingly found in the same crystal. These differ in
the orientation of attachment of the alkyne and would be interconverted
by an alkyne rotation. Isomers 49 and SO must be similar in energy and,
since a solution shows only a single Cp nmr resonance, their interconversion
seems to be rapidY24)
The compounds [HOs
3
(JL 3-C6H4) (CO)g(X)] (X = SMe(121) or
AsMe2 (122) are structurally analogous. Isomers related by S inversion
readily interconvert, while the even faster exchange of the Os-bound carbon
atoms A and B (Scheme 17) could occur by process 1 or 2, that is hydride
Scheme 17
til
A-a A-a
2
a-A
H_ ,
,
l _H
-
__ H
-
\ ;::05-......,:
-
,..........05 .......... I
-
........... 05, I
05 ............ /05 05 ............ /05 05 ............ /05
X X X
migration or C
6
H4 rotation. Using SCHMe2 for X the diastereotopic Me
groups exchange at the same rate as A with B, supporting process 1.
However, the diastereotopic Me groups in [HOS3(JL3-C6H3CHMe2)-
(CO)g(AsMe2)] also exchange at a similar rate to the interconversion of
diastereomers (equivalent to the exchange of A with B) and this supports
an aryne rotation but does not rule out a hydride migration. Possibly
processes 1 and 2 have similar rates or alternatively the hydride and aryne
motions are coupledY21,122)
The Me groups in [C0
3
(CO)g(CCHPr
i
)t are diastereotopic and aniso-
chronous at -60C which confirms a tilted rather than upright arrangement
of the ligand; 51 is a simple representation. The Me groups exchange (.::lO*

!-
CHMC
2

(COI,c( \ )oICOI,
Co
(COI
3
51
10.5 0.1 kcal mol-
1
) by an inversion at the carbon atom CCHPr
i
and
Scheme 18 illustrates diagramatically how this could be achieved by 60
rotations of the ligand with respect to the C0
3
triangle occurring together
with 90 rotations about the C-C bond. Probably the Pri group moves away
from the metal atoms in the intermediate state as shown. (127)
Scheme 18
-
-
A rather similar enantiomerization process for [HM
3
(CO)g(JL3-
MeC=C=CMe2)] is faster for M = Ru than for M = Os (Scheme 19). A
feature in common between Schemes 18 and 19 is that an approximately
Sp2 -hybridized carbon atom is turned over so that its opposite face is bound
as part of an 1'/2 linkage. A hydride shift must accompany the movement
of the allenylligand. (128)
Scheme 19
-
-
In the complexes of similar type such as [HRu3(CO)9
(CH=C=CNMe2)] there is a hindered rotation about the C-N bond, the
barrier of which has a distinct dependence upon the replacement of CO
by phosphorus(III) ligands at a distant metal atom. Since steric effects are
unlikely to be important the transmittance of electronic effects through the
cluster is discussed. (129) Rotation about C-N in the complexes
[HFe3(CO)g(CNR2)] is also restricted and an nmr study has been madeY30)
52
Finally the interconversion of the enantiomers 52 and 53 gives coales-
cence of the C02CHMe2 nmr signals (ao* = 13.1 0.6 kcal mor
l
). This
cannot be achieved by CO migration alone and either requires disruption
of the Co
3
C skeleton or the Co-P or Co-As bondsyo2l
Chapter 14
Homogeneous Catalysis of
Organic Reactions by
Complexes of Metal Ions
14.1. Introduction
Although this chapter concentrates on reports of kinetic studies on organic
reactions which are homogeneously catalyzed by transition metal com-
plexes, frequent references are made to other papers which provide an
insight into the mechanism of a particular reaction or which report
significant advances in the area under discussion.
14.1.1. General Reviews and Elementary Steps in
Homogeneous Catalysis
A key step in many catalytic reactions is (J'-7T' rearrangement; a review(1)
covering this topic is therefore particularly welcome, as is a discussion of
solute-solute and solute-solvent interactions in homogeneous catalysis by
transition metal complexes. (2) Criteria for deciding whether an active
catalytic species is a transition metal cluster have been reported(3) and the
factors controlling the selectivity in transition-metal-catalyzed organic reac-
tions have been discussed. (4) Reviews on phase transfer catalysis in
organometallic chemistry(5) and catalytic asymmetric synthesis(6) should
also prove to be of interest. Although it is strictly outside the scope of this
351
352
14 Homogeneous Catalysis of Organic Reactions
chapter, readers should be aware that an area of considerable research
activity is the production of hydrogen by irradiation of water in the presence
of transition metal complexes as photosensitizers; the present state of the
art has been reviewed. (7)
Reactive intermediates (t
1
/2 - 100 ms at >10-
2
M) may be observed
by rapid injection nmr spectroscopy;(S) this technique could obviously prove
invaluable in the elucidation of the mechanisms of catalytic reactions.
Nuclear magnetic resonance has also been used to demonstrate that a-H
elimination may be as facile as (3-H elimination; thus [Ta](CHBut)Et and
[Ta](CH2Bu
t
)(1)2-C2H4) ([Ta] = TaCb(PMe3h) have been shown to be in
equilibrium with each other, the equilibrium being established via a-
hydride elimination from the neopentyl group and (3 -hydride elimination
from the ethyl group.(9) Platinacyclobutanes are often used as models for
the labile metallacyclobutanes involved in catalysis. It is therefore pertinent
to note that the rearrangement of platinacyclobutanes to platinum-alkene
complexes [equation (1)] involves an initial a-hydride elimination rather
than a (3 -hydride elimination as reported previously. (10)
Me H
+ 2-Mepy ---+
DD
4
Cl CDH
2-Me
py
-+-1I (1)
Cl F\
Me CHDMe
14.2. Reactions Involving Carbon Monoxide
14.2.1. Hydroformylation and Hydrocarboxylation of Olefins
Recent developments in hydroformylation(1l) and the mechanisms of
Co-, Rh-, and Ir-catalyzed olefin hydrocarboxylations(12) have been
reviewed. The proceedings of a symposium on "Catalytic Activation of
Carbon Monoxide" should also prove useful to those readers who wish to
familiarize themselves with current areas of interest. (13)
It has been shown that uv irradiation of cobalt carbonyl species under
hydroformylation conditions does not lead to higher reaction rates and the
active catalytic species [COH(CO)4] may even be destroyed photochemi-
callyY4a) In contrast, similar irradiation of Co(OAc)z in methanol reduces
the induction period by enhancing the reduction to [Co(CO)4L irradia-
tion also promotes the hydroformylation of less reactive olefins such as
cyclohexene [equations (2)_(4)].(14b) With phosphine-modified cobalt
14.2 Reactions Involving Carbon Monoxide 353
[CO(CO)4r [Co(COhr (2)
-co
[Co(COhr + RCH=CH
z
---+ [CO(COh(l1z-CHz=CHR)r (3)
[CO(COh(l1z-CHz=CHR)r + H+ ---+ [Co(COhCHzCHzR]
---+ hydroformylation products (4)
compounds in methanol, irradiation enhances the formation of
[CoH(CObPBu3] [equation (5)], a very selective catalyst for the formation
[Co(COh(PBu3lzt [CoH(COh(PBu3)] + H+ + PBU3 (5)
2
of n -aldehydes from Q' -ole fins, e.g., propene 99% butyraldehyde. (14b.e)
Kinetic studies on the hydroformylation of C
ll
-C
I4
ole fins with
[COH(CO)4] + PR
3
(R = Bu", n-C
S
H17' n-C
12
H
zs
, or n-C
Is
H
3I
) have been
carried out to optimize the yield of linear fatty alcohols which are surfactant
precursors. (1S)
A kinetic study which takes account of possible gas-liquid mass-
transfer restrictions has been reported for the hydroformylation of
hept-l-ene in the presence of [Rh(nbd)Clh + PPh
3
Y6) Hydroformylation
of propene has been studied using [RhH(CO)(PPh
3
h] + PPh
3
;(17) the
catalyst undergoes appreciable degradation to form mainly
[Rh(COlzPPhz]n, Ph
3
PO and Pr(Phlzp.(17a) Surprisingly, the rate of butyral-
de hyde formation was found to be independent of both Peo and P
H
2
although the relative amounts of PPh
3
and CO did influence the n : iso
ratio of the butyraldehyde. (17b) The factors controlling the n : iso aldehyde
are obviously subtle. For example, in the [RhH(PPh
3
)4]-catalyzed hydrofor-
mylation of styrenes electron-withdrawing p-substituents favor the forma-
tion of the branched aldehyde, 2-aryl propanal, the opposite trend to that
observed when [RhCI(COlzh is the catalyst precursor.
iIS
) Also, in the
[RhCI(CO)L
2
]-catalyzed hydroformylation of hex-l-ene, n -heptanal is
favored by electron -withdrawing ligands [L = Ph
3
-
x
(NR
2
) x P 119a) or L2 =
Fe( l1s-CsH4PAr2h(l9b)] and by para alkyl substituents on the phosphine
[L = (p- RC
6
H
4
hP]' (lge) Studies on the hydroformylation of trifluoro-
propene and pentafluorostyrene indicate that the regioselectivity is very
dependent upon the nature of the central metal of the catalyst and it is
proposed that the stability of the branched alkylmetal intermediate increases
along the series
RfCH(Me)[Co] < RfCH(Me)[Pt] < RfCH(Me)[Ru]
< R
f
CH(Me)[Rh].120)
Several studies of phosphine-modified rhodium catalysts indicate that
three phosphorus atoms are coordinated to the rhodium at the instant that
354
the n : iso ratio is determinedY9b,21) For example, the selectivity in the
{[Rh(COhCIJz + nFe('T/ 5 -CsH4PAr2h}-catalyzed hydroformylation of hex-
l-ene shows no further change beyond n = 3Y9b) Also 31
p
nmr studies of
[RhH(CO)(PPh
3
h] in the presence of a wide range of chiral bisphosphines,
PP, indicate that the principal species present are [RhH(CO)PPh
3
(PP)],
[RhH(CO)(PPh.sJz and [RhH(CO)(PP)(unidentate pp)].(21a)
The use of platinum complexes for hydroformylation is an area of
growing interest. [Pt(ER
3
)(CO)Clz] + 2SnClz (E = P or As, R = aryl
or alkyl)-(22) and {[PtClz(NCPhh] + diphosphine + SnCh}-(23) catalyzed
hydroformylations of terminal alkenes are extremely regiospecific (i.e.,
:s99% linear aldehydes). The factors favoring the formation of linear
aldehydes in the {[PtCI(CO)(PR
3
ht + SnCI
2
}-catalyzed hydroformylation
of internal ole fins have also been examined. (24) Insight into the mechanism
of these hydroformylation reactions comes from the isolation of the active
intermediates [PtX(COPr")(PPh
3
h] (X = CI or SnCh) from the reaction
of cis -[PtClz(PPh
3
h] with propene and carbon monoxide in methanol. It
has been suggested that the Pt-Sn bond plays a key part in promoting the
formation of the aldehyde from the acyl derivative.(2S) However, a study
of the reactions of trans-[Pt(SnCh)(Ph)L
2
] (L = PPh
3
or PMePh
2
) with
CO indicates that the role of the SnC13 group is to provide a good leaving
group.(26)
The [Pt(diop)(SnCI
3
)CI] (diop = 1a)-catalyzed deuterioformylation
of Z - or E -but-2-ene proceeds with cis stereochemistry. (27) Using PtCh +
(-)-diop (1a) + SnCh, the rate of styrene hydroformylation is proportional
(1) a R = Ph
b PR'"Pd
1
to [Ptt
8
, p[H
2
]\ p[COnstyrene]O.3;(28a) this contrasts with that reported
for [PtCh(PPh
3
h]-SnCh, i.e., rate oc [Ptt
S
, p[H
2
]2, p[COro.
s
,
[styrene ]1. (28b) To date the optical yields obtained in asymmetric hydro-
formylation have been disappointing; however, remarkably high (:S 95%)
optical yields of (S)-( + )-2-phenylpropanal are obtained when styrene is
hydroformylated using PtCh + SnCh with the bis(dibenzophosphole)
analogue of diop (1b). Using diop (1a) optical yields are modest (:s36%
e.e.).(28a) Asymmetric hydroformylation of vinyl acetate with [Rh(cod)-
(acac)] + (1b) gives :s51 % e.e. of (R)-MeCH(OAc)CHO; again diop is
less effective (::;32% e,e.).(29)
14.2 Reactions Involving Carbon Monoxide
355
Carbonylation of alkenes in alcohols 10 the presence of
[PdCl
z
(PPh
3
h] + PPh
3
results in the formation of esters (i.e., hydro-
carbalkoxylation); the proportion of branched ester is increased by
adding a solvent to the alcohol, or on increasing Pea or in the presence of
LiCI. This has been rationalized by presuming that these factors favor
a less hindered catalytic species. (30) Kinetic studies and the effect of
additives have also been reported for [Co
z
(CO)8]-catalyzed hydro-
esterification reactions of CHz=CHCN, CH
z
=CHCO
z
Me,(31a) and
NC(CH
z
hOCH
z
CH=CH
z
(31b) carried out in methanol.
14.2.2. Decarbonylation of Aldehydes
The [Rh(dppph]BF
4
{dppp = 1,3-bis(diphenylphosphino)propane}-
catalyzed decarbonylation of benzaldehyde involves a rapid preequilibrium
with the formation of [Rh(dppph(PhCHO)]BF4 followed by the rate-
determining step, oxidative addition, to give [RhH{C(O)Ph}dppph]BF
4
.(3Z)
14.2.3. Carbonylation and Homologation of Alcohols, Halides,
and Nitro Compounds, Ethers, Carboxylic Acids,
and Esters
A kinetic study of the formation of phenylacetic acid by the carbonyl a-
tion of benzyl alcohol in the presence of RhCh 3HzO + PhCHzI supports
a mechanism analogous to that of methanol carbonylation, i.e., the rate-
determining step is the oxidative addition of PhCHzI to [Rh(COhlzr. (33)
Acetaldehyde is the initial product from the reaction of methanol with
CO/Hz in the presence of [FeC0
3
(COhzr + Mel; ir studies indicate that
the cluster breaks down to form the active species.(34) A similar reaction
of methanol in the presence of Coh + Ph2P(CH
2
)6PPh
z
yields ethanol
(selectivity::5 89%). (35) {3 -Hydrogen elimination is normally a strongly
competing pathway in carbonylation reactions of organic halides; however,
[PdClz(AsPh
3
h] successfully catalyzes the reaction of CO and SnMe4 with
organic halides having (3 -hydrogens, e.g., PhCH(Me)Br gives mainly
PhCH(Me)COMe rather than styrene.(36) Similar reactions of PhCH(R)Br
(R = H or Me) carried out with Na[Co(CO)4] under phase transfer condi-
tions lead to either PhCH(R)CH
2
Na and PhCH(R)COC0
2
Na or the
coupled products PhCH(R)CH(R)Ph; the mechanisms of these reactions
have been discussed.(37) Ruthenium compounds, e.g., [RU3(COhz], coupled
with alkyl or hydrogen iodide, catalyze the homologation of aliphatic
carboxylic acids [equations (6) and (7)](38) and the homologation of MezO
to MeC0
2
Et. (39)
+ CO + Hz ....... (6)
+ CO + Hz ....... (7)
356 14 Homogeneous Catalysis of Organic Reactions
Trivalent phosphorus compounds (e.g., PPh
3
) promote the homologa-
tion of methyl formate to ethanol and ethyl formate by ruthenium iodide
compounds (e.g., [Ru(COhI3n. The proposed mechanism for ethanol
formation is shown in equations (8)-(11). (40)
HC0
2
Me + HI ---. Mel + HC02H (8)
Mel + [Ruo] ---. [Me RullI] [MeCORuI] (9)
[MeCORul] + H2 ---. [HRul] + MeCHO (10)
MeCHO + H2 + [Ru] ---. C
2
H
s
OH + [Ru] (11)
In the presence of RhCh x H
2
0, Mel, an organic base and chromium
compounds, methyl acetate is carbonylated to acetic anhydride. The rate
is first order in rhodium, Mel, and, at low concentrations, the base;
chromium compounds have less influence on the rate but reduce the
induction period remarkably.(41) Catalytic carbonylation of nitro-
compounds has been reviewed. (42)
14.2.4. Fischer-Tropsch Reactions
Current mechanistic ideas on the homogeneous hydrogenation of
carbon monoxide are summarized in a number of useful reviews. (43) There
have been many attempts to gain an insight into the mechanisms of Fischer-
Tropsch reactions by studying the chemistry of model intermediates. For
example, full details of the stepwise reduction of the coordinated carbonyl
group of [ReCp(CO)NO(L)]"+ have been reported (i.e., n = 1, L =
CO ---. n = 0; L = CHO ---. L = CH
2
0H ---. Me)(44) and the reactions of the
formyl(4Sa-c) and hydroxomethyl(4Sc) intermediates investigated. Similarly,
[OS3(CO)12] is reduced by KBH(OPrih or LiBHEt3 to [(OCH)OS3(CO)l1r
which with H
3
P0
4
gives [Os3(CH
2
)(CO)11]; this in turn reacts with
hydrogen to give methane. (46) Evidence has also been presented that the
hydroxymethylidyne cluster [C03(lLrCOH)(CO)9] is an intermediate in
the cobalt-carbonyl-catalyzed hydrogenation of CO to methanol and C
r
oxygenated compounds. (47) The possible intermediacy of coordinated car-
benes in the reduction of CO to olefins is supported by the following
observed sequence of reactions(48):
[Cp2WH2] + [CpZr(R){C(O)R}] ---. [Cp
2
WH{IL-CH(R)O}Zr(R)Cp2]
(R = Me or Ph) (12)
[Cp2 WH{IL -CH(Ph)O}Zr(Ph)Cp2] ---. [Cp2 W=CHPh]
+ [Cp2Zr(OH)Ph] (13)
14.2 Reactions Involving Carbon Monoxide 357
[Cp
2
WH{I-'-CH(Me)O}Zr(Me)Cp2] -. [Cp2W(C
2
H
4
)]
+ "Cp2Zr(OH)Me" (14)
A key chain growth step in Fischer-Tropsch reactions may be the
insertion of a methylidene ligand into a metal-alkyl bond. Evidence has
been presented that such an insertion occurs in a transient tungsten-
methylidene methyl complex [equation (15)] and that this reaction becomes
highly favorable when the alkylidene center is electrophilic. (49)
(15)
Although the formation of formaldehyde from mixtures of H2 and CO
(Le., synthesis gas) is thermodynamically unfavorable it has been argued
that the concentration of formaldehyde permitted by thermodynamics is
more than sufficient for a transient intermediate. Further, all the products
derived from synthesis gas conversions can be rationalized by assuming
that they are formed via formaldehyde (Scheme 1). Support for this proposal
[MJ-H
Scheme 1
[M]-H + MeOH MeCHO EtOH, EtOCHO
A
[M]CH
2
0H

sY'
[M]OMe

[M]c(O)CH,OH [M]-H + HOCH,CH,OH
HOCH
2
CH
2
0H
HOCH
2
CH(OH)CHO
HOCH,CH,OCHO
[M]C(O)OMe [M]-H + MeOCHO
[M]-H + MeOH CH
4
comes from reaction rate studies, comparison reactions of formaldehyde
with synthesis gas, and the trapping of formaldehyde during a reaction as
1 ,3-dioxolane(50) [equation (16)].(50)
CH20 + HOCH2CH
2
0H -. CH
2
0CH
2
CH
2
0 (16)
The purported(51a) Fischer-Tropsch alkylation of benzene catalyzed
by [Mm(CO)n](M = Cr, W, Ru, Co, or Rh) in the presence of AICh is
simply the result of a Lewis acid-catalyzed cracking of benzene since similar
alkylations occur when benzene and AICh are heated together.(51b) It had
also been reported that cobalt carbonyls in glyme solvents catalyzed the
hydrogenation of CO(52a) but experiments carried out with 13CO now
indicate that >90% of the ethanol formed is derived from the solvent. (52b)
Similarly the trimethyl phosphite-enhanced formation of methane from
synthesis gas in the presence of [Ir4(COh2] or [Os3(COh2](53a) has been
shown to arise from a catalyzed reaction between hydrogen and
P(OMeh.(53b)
14.2.5. Homogeneous Water-Gas Shift Reaction (WGSR)
The use of ruthenium and other metal carbonyl catalysts has been
reviewed.(54) Kinetic studies suggest that the M(CO)6-KOH (M = Cr>
W> Mo)-catalyzed WGSR reaction involves formate decomposition
(Scheme 2). (55) Support for this proposal comes from the isolation of the
formate complex (2, M = Mo) from the catalytic mixture(56) and from the
reaction of carbon dioxide with the corresponding hydride anion (3, M = Cr,
Mo, or W). (57) The active catalyst [W (CO h] can be generated by photolyzing
[W(CO)6]. (58)
Scheme 2
+co
HC0
2
-
+H,ot-[M(CO),J
'I-H,
l[M(CO),J
[M(COMHC0
2
)r
2
The mechanism of the [Fe(CO)s]-catalyzed WGSR in alkaline solution
is believed to be that shown in equations (17)-(20). Kinetic studies of
reactions (17) and (19) have been carried out and it has been pointed out
that [Fe(COh] is a poor WGSR catalyst because of the conflicting pH
[Fe(COh] + OH- [HFe(CO)4r + CO
2
[HFe(CO)4r + H
2
0 [H2Fe(CO)4] + OH-
(17)
(18)
14.3 Oxidation
[H
z
Fe(CO)4] Hz + [Fe(CO)4]
[Fe(CO)4] + CO --+ [Fe(CO)5]
359
(19)
(20)
requirements of reactions (17) and (18).(59) Kinetic studies have shown that
[Ru(CO)s] is considerably more susceptible to hydroxide attack than
[Fe(CO)s]; this could explain why the former is the more efficient WGSR
catalyst in alkaline solution.(60) [RU3H(CO)l1r has been shown to function
as a hydride donor in the presence of CO; this suggests alternative mechan-
isms for the [Ru3(CO)u]-catalyzed WGSR in basic solution [equations
(21)-(24)].(61)
[RU3(CO)u] + --+ [Ru
3
H(CO)l1r + CO
z
(21)
[RU3H(CO)l1r [RU3(CO)u] + (22)
+ HzO --+ Hz + (23)
[RU3H(CO)12r + H20 --+ Hz + + [RU3(COh2] (24)
Rhodium(I)-hydrido compounds, e.g., in pyridine, serve
as catalyst precursors which effect the WGSR under mild conditions
(s100C, Pea 20 kg/cm\ Chemical studies of the key intermediates indi-
cate that the main catalytic cycle is that shown in Scheme 3.(62)
Scheme 3
H,O
P7
eo
-H/
trans-[Rh(CO)S(LhlOH
+H,O
[RhH
2
(CO)S(LhlOH trans-[RhH(CO)L
2
1 ==:. [Rh(C0
2
H)CO(Lhl
L2 = PPr'3, S = solvent (e.g., py)
14.3. Oxidation
A detailed account of the mechanisms of catalytic oxidation processes
has been published. (63) The mechanisms of the catalytic oxidation of ter-
minal olefins to methyl ketones(64) and of the catalytic epoxidation of olefins
with hydroperoxides have also been reviewed. (6S) The latter reactions are
generally thought to proceed via direct attack of the substrate upon an
electrophilic oxygen of a metal peroxo species rather than prior complexa-
tion of the substrate to the metal complex. For example, [Mo(TPP)O(OMe)]
(TPP = tetraphenylporphyrin) catalyzes the selective epoxidation of
olefins by ButOOH and it has been argued that owing to the steric hindrance
of the macrocyclic ligand simultaneous coordination of the olefin and the
hydroperoxide to the metal center would be unlikely.(66) Kinetic studies
on the [Mo0
2
(acach]-catalyzed oxidation of p-ClC
6
H
4
SMe with hydrogen
peroxide to give the corresponding sulfoxide also support direct attack
upon an electrophilic oxygen(67) although no firm conclusion could be
reached for the corresponding [TiO(acach]-catalyzed oxidation by
But OOH. (68) Insight into the nature of the intermediates in V(V)-catalyzed
oxidations comes from kinetic and spectroscopic data which indicate that
alkyl peroxides react with vanadium(V) compounds to give vanadium
peroxo ester intermediates [V]OOR whereas hydrogen peroxide produces
vanadium(V)-sidebonded peroxo complexes [V]o6. (69) An interesting
example of a kinetic resolution involves the Ti(OPr
i
)4-( + )-diisopropyl tart-
rate promoted asymmetric epoxidation of allyl alcohols with But OOH.
With racemic alcohols, erythro epoxides are strongly favored; thus (5)-
(C
6
H
ll
)CH(OH)CH=CHMe reacts 104 times faster than the R-enan-
tiomer to give an erythro:threo ratio of 98: 2 and to leave the unreacted
R-enantiomer in The epoxidation of maleic acid by hydrogen
peroxide in the presence of tungsten acid H2 W0
4
or its salts is first order
in substrate, H
2
0
2
, and catalyst.
17
!)
The controversy over whether manganese(II) halide-tertiary phos-
phine systems are reversible dioxygen carriers continues. (72) Oxidation
of triphenylphosphine by [Ru
1v
e
8
0)(bipyhpy f+ proceeds via
[Ru"(180PPh3)(bipyhpy]2+ and gives 180PPh3 quantitatively.(73) Kinetic
studies on the radical pathways involved in the cobalt(II)-catalyzed autoxi-
dation of polyalkylated aromatic hydrocarbons
(74
) and the [Co(tetra(p-
tolyl)porphyrin)]-l75a) or [Fe(C
s
H
s
h]-17Sb)catalyzed autoxidation of
aldehydes to acids have been reported. Lewis acids (e.g., BF30Et2 or LiPF6)
activate cobalt-nitro complexes such as [Co(TPP)py(N0
2
)] (TPP =
tetraphenylporphyrin) or [Co(saloph)py(N0
2
)] [saloph = N,N'-bis-
(salicylidene )-o-phenylenediamino] to oxidize primary or secondary
alcohols to aldehydes or ketones. The role of the Lewis acids is to bind to
the nitro ligand and thus increase its electrophilicity; in addition, they
facilitate reoxidation of the nitrosyl complexes by dioxygen.(76) Similarly,
[Pd(MeCNbCl(N0
2
)] catalyzes the air oxidation of dec-l-ene to decan- 2-
one; IRO-labeling experiments have shown that the reaction involves oxygen
transfer from the nitro group and, in the analogous oxidation of propene to
acetone, the intermediate [PdCHCH(Me)ONO(MeCN)Cl] derived from
attack of the nitro group on the coordinated propene has been detected. (77)
Rate studies on the [RhX(PPh
3
h]-catalyzed (X = CH, OCN, or SCN)
cooxygenation of oct-l-ene and triphenylphosphine have been reported.
14.3 Oxidation 361
Although the detailed mechanism is unknown, the first step is believed
to involve formation of the corresponding peroxo-complex [RhX-
(PPh3h02].(7S) The [IrHCh(C
s
H
12
)]z-catalyzed cooxidation of cyclooctene
and hydrogen [equation (25)] is believed to proceed via oxygen atom
transfer to cyclooctene from [Ir(00H)Ch(C
s
H
12
)].(79)
(25)
Kinetic and spectroscopic studies of the Pd(II)-catalyzed oxidation of
ethylene in acetic acid have been reported; the various products arise from
intermediates of the type [PdXX
I
(L)CH
2
CH
2
0Acr (X, Xl = CI, OAc,
L = O
2
, ONO, CI, or OAc) and the factors influencing the product distribu-
tion have been discussed.(SO) Oxidation of cyclohexa-l,3-diene using
benzoquinone + Pd(OAc)z + LiOAc in acetic acid gives> 90% trans-l,4-
diacetoxycyclohex-2-ene whereas, upon addition of LiCI, >93% of the cis
isomer is formed. This suggests that chloride blocks the coordination of
acetate to the palladium and hence external acetate attacks the 4-exo-
acetoxy-1-3-1/ -cyclohexenylpalladium intermediate to yield the cis
isomer. (S1) Similar arguments have been advanced to reaffirm that the
Wacker process could still proceed via cis attack of coordinated hydroxyl
in [PdCh(OH)(C
2
H
4
)r despite the stereochemical studies carried out at
high chloride and CuCl
2
concentrations which show that trans -hydroxypalla-
dation occurs.(S2) The observation that [PdCh(PhCN)Z]-CuCh catalyzes
the oxidation of hexa-l,5-diene to acetone has prompted the suggestion
that 1/ 3 -allylic intermediates are involved in the Wacker oxidation of
propene and higher alk-l-enes to ketones.(S3) Kinetic studies on the
{PdS04 + H9PM06V604o}-catalyzed oxidation of oct-l-ene to octan-2-one
(selectivity = 95%) have also been reported. (S4)
The air oxidation of substituted catechols to the corresponding 0-
benzoquinones is catalyzed by a variety of Cu(II)-amine systems. (85) It
appears that the mechanism involves the formation of a dicopper(II)
catechol ate intermediate; electron transfer then occurs from the aromatic
ring to give the 0 -benzoquinone and two Cu(I) centers. The latter then
react with dioxygen and the catechol to regenerate the dicopper(II) catecho-
late. (S5a) A study of the effect of chloride ions on the kinetics of the
copper-catalyzed oxidation of ascorbic acid by dioxygen does not rule out
the involvement of Cu(I) intermediates but a mechanism involving Cu(II1)
is preferred. (S6) Kinetic studies on Cu(II)-catalyzed oxidation of enamines
[e.g., equation (26)](S7) and 3-phenylpropanal(SS) have been reported.
14.4. Hydrogenation
Although the search for even more active and selective catalysts
continues, it is encouraging that increasingly spectroscopic techniques,
especially nmr, are being applied to investigate the nature of the catalytic
intermediates. This is particularly true for rhodium-catalyzed asymmetric
hydrogenation reactions where the intimate mechanisms are often known
in considerable detail.
14.4.1. Hydrogenation of Alkenes
Terminal alkenes are selectively and rapidly hydrogenated under
ambient conditions in the presence of [CoMe(COh{P(OMehh] (450 turn-
overs h -1); the proposed mechanism involves the generation of a free
coordination site by the reversible conversion of -Me to -COMe.(89)
Kinetic and mechanistic studies of the [CoX(bipyh]-catalyzed (X = halo)
hydrogenation of nonbranched 1,3-diolefins to mainly cis-2-0Iefins are
consistent with a mechanism involving anti -1-methyl-71
3
-ally1cobalt inter-
mediates. (90)
Theoreticaf
ll
) and experimental(92) studies of the mechanism of hydro-
genation of alkenes with [RhCI(PPh
3
h] have been reviewed. A similar
mechanism is believed to operate for the supported analog prepared by
reacting [RhCI( cod) h with phosphinated polystyrene. (93) Kinetic studies
have been carried out on the catalysts [Rh(cod)CI]2 + 4L [L =
(EtOhSi(CH2)nPPh2, n = 1-6, or (EtOhMeSi(CH
2
)mPPh2, m = 1-3] and
their heterogeneous silica-linked analog. It appears that deactivation occurs
via dimerization of the catalytically active species since the activity of the
heterogeneous catalyst decreases as the ligands become more flexible, i.e.,
as n or m increases. (94) Details on the nature of the intermediates involved
in Rh(I)-catalyzed hydrogenations come from nmr studies which show that
complexes of the type [Rh(diene)L
2
]BF
4
[L = monophosphine but not
P(o -MeOC6H
4
)Ph(Me)] react with hydrogen in polar solvents to give stable
dihydrides [RhH
2
L
2
(solv ht ; when L2 = cis -chelating biphosphine, solvate
complexes with no affinity for hydrogen are formed. (95) Other 13e and
31
p
nmr studies on [Rh
6
(CO)u{P(OPhh}4] have shown that the onset of
fluxional motion of some of the carbonyl ligands between triply bridging
and edge-bridging positions parallels the appearance of catalytic activity
for cyc10hexene hydrogenation. (96)
The rate of hydrogenation of terminal olefins with [RhCl-
{PhP([CH
2
hPR
2
h}] + Et
2
AICI is independent of [olefin] when R =
Ph but not when R = C
6
H
ll
.(97) A kinetic study of hydrogenation of
cyc10hexene catalyzed by [M
2
ChL] (L = C6H4[CH2P(CH2CH2EPh2h]2;
M = Rh, E = P or As; M = Ir, E = P) has been reported; the first step in
14.4 Hydrogenation 363
the catalytic cycle involves activation of hydrogen to form [M
2
C}zH
4
L].(98)
An interesting cooperative effect has been observed; a mixture of 80%
[{(Rh(T/ s -CsMes)h(JL -OHh]CI and 20% [Rh(cod)Clh generates a
homogeneous catalyst whose activity is approximately twice that of the
individual components.(99) The proposed mechanism for the trans-
[Rh(OH)(CO)L
2
]-catalyzed reduction of methyl crotonate with CO and
H
2
0 is shown in Scheme 4 (L = Hydroformylation becomes
dominant for olefins with less electron-withdrawing substituents, e.g.,
PhC(Me)=CH
2
...... PhCH(Me)CH
2
CHOYoO)
Scheme 4
Stepwise transfer of hydrogen is generally accepted although rarely
directly observed. An exception is the reaction of the carboranyl complexes
[Ir(H)z{7-Ph-l,7-C2BlOHlOHCO)RlCN(PPh3)](Rl = Me or Ph) with acti-
vated olefins and acetylenes such as R
2
CH=CHR
2
and R
2
C_CR2 (R
2
=
C0
2
Me). At room temperature the corresponding hydridoalkyl- or
hydridoalkenyl-iridium(III) complexes are formed and on warming these
reductively eliminate alkane or alkene, respectivelyYl) Kinetic studies
of the hydrogenation of cyclopentadiene with PdCIz + NaBH4 +
polyethylenimine, {CH
2
CH(=NH)}",(102) and of cyclopentene with
[Pd
s
(PPh)ZJn(103) have been reported. In reductions with LiAIH4 one
hydrogen normally comes from the LiAIH4 and the second from the
hydrolysis reaction in the work-up; in contrast UCh catalyzes the reduction
of C
2
H
4
by LiAlD4 to give C2H4D2Y04)
14.4.2. Hydrogenation of Arenes and Functional Groups
Muetterties has summarized his work on the hydrogenation of arenes
and alkynes with cobalt-phosphite catalysts. (lOSa) [CoH{P(OMehhJ rather
than an 17 1 -allylcobalt species is now believed to be the true catalyst in
hydrogenations carried out with [Co( 17
3
-C
3
Hs){P( OMe)3h]. (IOSb) The
31
p
nmr chemical shifts of OPR
3
correlate with the ligand basicity of the
phosphine PR3 and also with the activities of the catalysts [Mn2(CO)g(PR3h]
for anthracene hydrogenation. (106)
A kinetic study of the hydrogenation of nitrobenzene to aniline in the
presence of diaquacobaloxime and morpholine led to the suggestion that
the active catalyst is PhN02[Co(dmgHh(CH2CH20CH2CH2NH)hy07)
[Rh
6
(COh6]-y-aminopyridine systems catalyze the reduction of nitroben-
zene to aniline using CO + H
2
0 at atmospheric pressure; this hydrogena-
tion does not proceed via a water-gas shift reaction since the corresponding
reduction with hydrogen gas is considerably slower.(108) [Rh
6
(COh6](109)
and (110) both catalyze the hydrogenation of benzal-
dehyde and kinetic evidence has been presented in favor of hexa-
nuclear rhodium and diplatinum active species, respectively. [Rh(nbd)-
(PEt3h]CI04 is an efficient catalyst for hydrogenating ketones;
PhCH
2
COMe is particularly reactive and this has been ascribed to an
interaction of the rhodium with the arene ringY 11a) In the presence of
water this catalyst also hydrogenates PhCHCH
2
6 to PhCH
2
CH
2
0H.(111b)
The rate of hydrogenation of benzil, (PhCOCOPh), with [Co(dmgHh'
2H
2
0] + amine depends strongly on the structure and basicity of the
amine; this has been interpreted as evidence of heterolytic activation of
hydrogenY 12) A kinetic study of the [RuHCI(CO)(PPh
3
h]-catalyzed
hydrogenation of aldehydes to alcohols has been reportedY
13
) In
trifluoroacetic acid the [Ir(PPh3)nHm] (n = m = 3; n = 2, m = 5)-
. f k (114a) CO I fi (114b)
catalyzed hydrogenations 0 etones, Ph
3
H, or 0 e ns are
believed to proceed via hydride transfer from the catalyst to the protonated
ketone or carbocation.
14.4.3. Asymmetric Hydrogenation
A general review(11S) and one dealing specifically with mechanistic
studies of rhodium-catalyzed asymmetric hydrogenations(116) have been
published. Guidelines for the design of effective chiral ligands have also
been presentedY 17)
The vast majority of studies have utilized chiral phosphine ligands;
however, these are not generally successful for nonfunctionalized olefins.
It is therefore of interest that the systems of the type [Ti{17s-CsH4(-)-
menthyIH17S-C5H4R1)C!z] + LiAlH
2
(OR
2
h {R1 = (-)menthyl, H, or Me;
R2 = CH
2
CH
2
0Me, But, or (-)menthyl} catalyze the hydrogenation of
2-phenylbut-l-ene, albeit with low (:s;28%) enantiomeric excessY
18
) The
chiral amino carboxamide (S,S,R)-PhCH(NMe2)CH(OAc)-
CONHCH(Me)Ph in the presence of [Co(dmg)2(PPh
3
)] effects the hydro-
genation of CH
2
=C(NHAc)C0
2
Me with 34.5% e.e.; enantioselectivity is
believed to arise from hydrogen bonding between the substrate and the
amide group of the chiral amino carboxamide. (119)
Extended X-ray absorption fine structure spectroscopy has been
applied to obtain structural information on intermediates in solution in
Rh(I)-catalyzed asymmetric hydrogenationsY20) Further information
comes from 31
p
nmr studies which have shown that the enamides PhCH=
C(NHCOPh)C0
2
Me bind selectively to rhodium complexes of (4a) whereas
itaconic acid derivatives CH
2
=C(C0
2
R I)CH
2
C0
2
R
2
bind weakly, the
reverse being true for complexes of (4b). (121) The kinetics of the
PhzP

I
COR
a R = Ph
b R2 = OBu'
4
[RhH{( + )dioph]-catalyzed (diop = 1a) hydrogenation of styrene are con-
sistent with an "unsaturate" mechanism with one of the diop ligands
adopting unidentate binding. When the substrate is itaconic acid, 37% e.e.
and 60% e.e. are obtained at 20C and 80C, respectively. This unusual
result has been rationalized by assuming that a more effective mono-diop
catalyst is present at the higher temperatureY
22
)
5
[Rh(cod)(2R,4R -dioxop)]Cl0
4
(dioxop = 5) catalyzes the hydroge-
nation of dihydropeptides PhCH = C(NHCOR
1
)C(O)NHCH(R
2
)C0
2
R
3
but the enantioselectivity is very dependent upon the chiral center in the
substrate(123a) and the experimental conditions.(123b) Comparison of c.d.
spectra shows that the isolated diastereomer of the initial catalyst-substrate
adduct in the [Rh{S,S- Ph
2
PCH(Me)CH(Me)PPh
2
}t -catalyzed hydrogena-
tion of (Z)-PhCH=C(NHAc)C0
2
Et is also the major diastereomer in
I
solution and confirms that the prevailing chirality of the product originates
from the minor diastereomer because it is more reactive toward hydro-
gen. (124) The importance of the ring conformation of bidentate phosphines
in determining optical yields is demonstrated by comparing the hydrogena-
tions of R
1
CH=C(CO
z
H)NHCOR
z
with [Rh(nbd)L
z
]CI0
4
{L
z
=
Ph
z
PCH(Me)CH
z
CH(R
3
)PPh
z
, R3 = H or Me}. Complexed Lz (R
3
= Me)
adopts a skew conformation with two equatorial methyl groups and this
conformation orientates the phenyl groups in a chiral array; in contrast L
z
(R
3
= H) probably adopts an achiral chair conformation and the phenyl
groups are not in a chiral array. In keeping with this, the former gives high
optical yields e.e.), whereas the latter is ineffective % e.e.). (lZ5)
Similar Rh(I)-catalyzed reductions of RCH=C(NHAc)COzMe (R = Pr
n
and Pri) have been carried out with phosphines in which a C
n
chiral unit
separates two achiral P atoms; when n = 2 Z substrates are hydrogenated
more slowly and more enantioselectively than the E isomers but when
n = 4 the reverse is trueYZ6)
14.4.4. Hydrogen Transfer and Dehydrogenation Reactions
Hydrogen transfer to carbonyl-, azamethine-, and nitro-groups has
been reviewed. (1Z7) It is particularly interesting that in the presence of the
hydrogen acceptor, t -butylethylene, [ReHs(PMezPh)z] dehydrogenates
cyclopentane to give [Re( 11-CsHs)H
z
(PMe
z
Ph)]. (lZ8)
trans-[W(dpeh(Nzh] catalyzes the reduction of aromatic diazo com-
pounds ArNzCl by alcohols to give arenes ArH; the rate-determining step
is the cleavage of the C(a )-H bond in the alcohol. (lZ9) Ketones are reduced
to the corresponding alcohols by secondary alcohols in the presence of
[Ru(CF
3
CO
z
)zCO(PPh
3
h]; the equilibrium constants of these hydrogen
transfer reactions compare reasonably well with those calculated from the
oxidation potentials of the ketones. (130) Kinetic studies on the hydrogen
transfer from alcohols to benzylideneacetone (PhCH=CHhCO in the
presence of [RuClz(PPh
3
h] (6) have been reported. The mechanism invol-
ves conversion of 6 by the alcohol into [RuH
z
(CO)(PPh
3
h], which then
hydrogenates the olefinic bondY31) The [Ru3(CO)u]-catalyzed reaction
(27) is believed to proceed via hydrogen transfer from the hemiacetal
intermediate RCH(OH)OCHzR. (132)
RCHO + RCHzOH + PhC CPh --. RCOzCHzR + PhCH=CHPh
(27)
The influence of the competition between the donor and the acceptor
for the catalyst upon the rate of the [RhH(PPh
3
)4]-catalyzed reduction of
a,,B-unsaturated ketones by alcohols has been investigatedY33) [Ir(3,4,7,8-
Me4phen)(CzH4)zCI] + KOH is extremely active in transferring hydrogen
from alcohols to unsaturated substrates (e.g., PhCH=NPh, 5000 cycles
min-
1
at 83C). (134) The related catalyst [IrL
z
(cod)]CI0
4
+ KOH [L
2
=
chiral Schiff base, e.g., (+)-PhCH(Me)N=CH(2-py)] appears to be more
stereospecific than other catalysts for asymmetric hydrogen transfer; pro-
chiral ketones (e.g., PhCOPr) are reduced by propan-2-01 with ::533%
e.e. (135) The influence of parameters such as added chloride or acid and the
[Sn(II)]:[M(III)] ratio {M(III) = RhCh 3H
z
O, IrCh 3H
z
O, or H
3
IrCI
6
} on
the rate and stereoselectivity of the {M(III) + SnClz 2H
z
O}-catalyzed
reduction of cyclohexanones with propan-2-01 has been reported. (136)
Scheme 5
L OCOCFa
"'-/
Pd
L/ "oOH
Oxidative dehydrogenation of cyclohexanones with [Pd(CF
3
CO
z
h] is
believed to occur by the mechanism shown (Scheme 5) in which the pal-
ladium remains in the + II oxidation state throughout. (137) A related
mechanism has been proposed for the [Pd
5
(PPhh]-catalyzed oxidative dehy-
drogenation of cyclohexene to benzene.(13S)
14.5. Isomerization Reactions
14.5.1. Olefin Isomerization
Irradiation of [Fe(COh] or [Fe3(COh2] with laser light generates an
extremely active olefin isomerization catalyst; Fourier-transform infrared
measurements have shown that the lifetime of the active catalytic species
increases with olefin concentration from -7 s in a 20% solution to 30 s in
neat olefin. (139) Isomerization of 4-methyl pent-l-ene, L, occurs in the
presence of [CoH(N2)(PPh
3
h]; kinetic studies suggest that the active
catalytic species are [CoH(N
2
)L(PPh
3
h] and [CoHL(PPh
3
h] at high and
low nitrogen pressure, respectivelyY40) An alternative mechanism for the
catalytic isomerization of ole fins by Pd(II) compounds has been presented
and involves an electrophilic attack by Pd(II) on the 1T bond to give an
incipient carbocation species (Scheme 6).(141)
Scheme 6
R
R
[PdHj

[PdHj
R
rr
1
R R

(
[Pd+j + H+ [Pd+j
The rate of isomerization of hept-l-ene by PdClz has been found to
be first order in olefin and two-thirds order in PdClz, (142) whereas the
([RhCI(PPh
3
h]-SnClz)-catalyzed isomerization of Me02CCH2C(=CH2)-
C0
2
Me showed second-order kinetics in ester and rhodium complex. (143)
After partial isomerization of racemic alkenes, RCH(Me)CH(Ph)-
CH
2
CH=CH
2
(R = H or Me) by bis(N,N -methylsalicyaldimine)Ni +
+ L (L = diop, N,N-dimethylbornylamine, or N,N-dimethyl-
menthylamine) both the product alk-2-enes and the unreacted alkene are
slightly optically active (e.e. :::;2.45%). (144) In contrast, spectacular enan-
tioselectivity (:::;96% e.e.) has been obtained in the [Rh{( + )-binap}cod]CI04
{binap = 7}-catalyzed isomerization of N,N -diethylnerylamine (8) to N,N -
14.5 Isomerization Reactions 369

MeH
""'" t' :?' NEt2
NEt2
I I
7 8 9
diethylcitronellal-(E)-enamine (9). It is interesting to note that on replacing
binap with diop (la) only :::;26% e,e. was obtained.(145)
14.5.2. Skeletal Rearrangements
In chloroform, the rhodium catalyst for the isomerization of quadri-
cyclane to norbornadiene [equation (28)] is derived from [Rh(nbdhCI],
whereas in CCl
4
or toluene it appears to be derived from [Rh(nbd)Clh. (146)
(28)
[Pd(PPh
3
)4] effects the rearrangements of unsaturated 1,4-epiper-
oxides [equation (29)]; the conversion to 4-hydroxy enones (10) is thought
to proceed via Pd(O)/Pd(II) intermediates, whereas a radical process involv-
ing Pd(O)/Pd(l) interchange leads to the formation of syn -diepoxides (11)
and 1,4-diols (12).0
47
)

R
10
+ +
07
(29)
R R
11 12
The mechanisms of the [Pd(PPh
3
)4]-catalyzed conversion of 2-allyl-
azirines to pyridines and pyrroles, e.g., equation (30),(148) and the Pd(O)-
catalyzed 1,3-oxygen-to-carbon alkyl shifts, e.g., equation (31),(149) have
been studied in detail.

Me
Ph--(NJrMe PhQN
J--J+ I
Me Me
(30)
0-(yc(Me)R-+
(31)
Hexa-l,5-diene is catalytically converted into acetone in an aqueous
solution of [PdCh(PhCNh] and CuCh in the presence of dioxygen. This
has prompted the suggestion that the [PdCh(PhCNh]-catalyzed Cope rear-
rangement of acyclic 1,5-dienes could proceed via 1/ 3 -allylic intermediates,
as in equation (32).
k7
'" / *
Pd
/"'..
CI CI
/'

Pd
/ "'..
CI CI
,
4-l7
" / *
Pd (32)
CI/ 'cl
,
Insight into the mechanisms of the [PtCh(C2H4)]2-catalyzed rearrange-
ment of bicydo[1.1.0]butane 13 comes from the isolation of 14 when the
catalytic mixture is treated with two equivalents of pyridineY50)
py"l4

CI
<1>
13
14
14.6. Alkene and Alkyne Metathesis
Recent developments and applications of metathesis reactions have
been reviewed(151) and also discussed at a symposiumys2)
Undoubtedly the most significant recent result is the direct observation
of the chain-carrying carbene complex in an alkene metathesis reaction.
Thus, interaction of [WO(OCH
2
Bu
t
h(CH
2
Bu
t
h] with AlBr3 yields initially
the adduct [W(OAlBr3)(OCH2Buth(CH2Buthf53a) and then the carbene
complex [W(CHBut)(OCH2ButhBr2] together with (AIOBr)n and Bu'Me.
Addition of a further mol. equivalent of AlBr3 generates an extremely
active metathesis catalyst [W(CHR)Br(BrAlBr3)(OCH
2
Bu
t
h] (15, R =
But) characterized by IH and BC nmr. That this is the active catalyst was
14.6 Alkene and Alkyne Metathesis 371
shown by the addition of cis-MeCH=CHEt; the initial carbene reson-
ances decreased with the concomitant appearance of signals corresponding
to the new chain carrier i.e., 15, R = Me or Et. Further, the reaction
mixture contained both products of initiation (i.e., ButCH=CHMe and
ButCH=CHEt) and metathesis (i.e., but-2-ene and hex_3_ene)Y53b)
Pathways leading to the formation of metallocarbene initiators from
the reactions of main group metal alkyls with transition metal chlorides
have been investigated. (154) For the metathesis catalyst Ah03 +
[W(COhX
2
(EPh
3
h] (X = CI or Br, E = P or As) the formation of the
initiating-carbene species has been linked with the conversion of coordin-
ated CO into organic carbonyl derivatives. (155) There has been considerable
discussion about the geometrical and electronic features of metallacyclo-
butanes and other proposed intermediates in metathesis reactions. (156) In
particular the ring strain in platinacyclobutane rings has been shown to be
much smaller than in cyclobutane. (157) This may explain why metalla-
cyclobutanes are more important as intermediates in organic chemistry
than cyclobutanes are in organic reactions. With regard to electronic effects
the activity of the metathesis catalyst [W(OAr)4Ch] is enhanced by factors
which would reduce the amount of 1T' bonding to the tungsten either by
the presence of electron-withdrawing groups in the 4 position of the
phenoxide or by the presence of ortho substituents which presumably force
longer W-O bond lengths. This suggests that the reactive carbene inter-
mediate is electrophilic in nature. (158)
Results of an ab initio theoretical mechanistic study indicate that
oxo-alkylidene complexes are the active chain-carrying metathesis catalysts
for high valent Mo, W, and Re complexes and that the oxygen ligand
stabilizes the metallacycle intermediate. (159) Traces of dioxygen do, in fact,
often enhance the activity of metathesis catalysts but this has been ascribed
to the formation of metallaoxacyclobutanes [M]-OCHRtHR
1
which
break down to give the initiating metallacarbenes. (160)
Support for the idea that the mechanism of alkyne metathesis is
analogous to that generally accepted for alkene metathesis, i.e., equation
(33), comes from the observation that the carbyne complex [W(CBu
t
)
catalyzes the metathesis of Ph
I3
C=CC
6
H
4
Me-p to give
Ph
I3
C=
13
CPh and p-MeC6H4C=CC6H4Me-pY61) Further, the carbyne
complex [W(CBut)(OButhJ reacts with diphenyl acetylene to give
PhC=CBu
t
and the new benzyne complex [W(CPh)(OBu
t
hf
62a
); the rate
of the latter reaction is first order in both acetylene and tungsten complex.
It has also been shown that the metathesis of PhC=CEt by [W(CBu
t
)-
(OBU
t
)3] is slower than either the metathesis of PhC=C(Tol) or PrC=CEt
because the intermediate benzyne complex, [W]=CPh, reacts with
PhC=CEt in a largely degenerate fashion (i.e., exchange of benzyne)Y62b)
[Mo02(acach]-AlEt
r
PhOH is a very active homogeneous alkyne meta-
thesis catalyst. The phenol is believed to weaken the alkyne bond by
hydrogen bonding interactions and also, being acidic, it promotes isomeriz-
ation of the metallacyclobutadiene intermediates, i.e., 16 17 via H+
addition to 16 and subsequent rearrangement of the cationic 7T-allyl inter-
mediate to 17, as in equation (33).0
63
)
[M]=CRI
Rl Rl
[M]-CR2
+
-----'"-
[e( ----'"-
[n

+
----

R2C=CR3
RIC=CR3
R2 R3 R2 R3
16 17 (33)
Considerable variations in stereo selectivity are observed in different
h
. d f h' . (164-167) Th
metat eS1S reactlOns an attempts to account or t 1S contmue. us
it has been suggested that if the coordinated olefin has an energy which is
smaller than that of the two possible metallacyclobutanes which lead to
the cis or trans isomers the resulting stereoselectivity will be governed by
the energy levels of these two metallacyclobutanes. If, however, the coor-
dinated olefin has an energy which is higher than that of the cis - and
trans -directing metallacyclobutanes the system will lose its stereoselectivity
and give a trans: cis ratio of unity. Most acyclic ole fins belong to the first
category, whereas highly strained olefins belong to the second. This explana-
tion implies that the ligands of the precursor complexes do not govern the
Scheme 7
+ AIMe
2
Cl
Y But f Y 'But
II D Me2AI-CI II D
trans-(18-d \)
1l
R
CP2Ti!;AIMe2 + ButC=CHR
Cl
(R = H or D)
14.7 Oligomerization and Polymerization of Alkenes and Alkynes 373
stereoselectivity by their own steric requirement but rather by their elec-
tronic effect on the stabilities of the metallacyclobutane intermediates. (165)
In contrast, the stereoselectivity observed in the cross-metathesis of oct-l-
ene with cis- or trans-oct-2-ene catalyzed by WCI
6
-SnPh
4
, W(OPh)6-
EtAIClz, or WCI6-EhAI has been rationalized in terms of minimizing the
interactions in the tungstacYclobutane intermediate between the alkyl sub-
stituents on C(2) and the tungsten in the 4 position of the ring. (166) It should
be noted, however, that reaction of the titanacyclobutane trans-(18-d
1
)
with Me2AICI resulted in rapid scrambling of the stereochemistry of the
a carbon of the metallacYcle to give equal amounts of cis - and trans- (18-d 1)
before cleavage to give neohexene-d
1
and -do. The proposed mechanism
involves a rapid reversible transmetalation at the Ti-C bond (Scheme 7).
Hence the tendency of a given metathesis catalyst to show high stereo-
specificity may depend upon the steric and electronic factors which deter-
mine the susceptibility of the metallacyclobutane intermediate to trans-
metallation by any Lewis acid cocatalyst present. (167)
14.7. Oligomerization and Polymerization of
Alkenes and Alkynes
14.7.1. Reactions of Alkenes
Mechanistic studies of Ziegler-Natta polymerization have been
reviewedY68) [Lu(1J5-C5Me5hCH3(Et20)] reacts with propene-d
6
to give
CD
2
=C(CD
3
)CH
3
and, after hydrolysis, CHD
2
CD(CD
3
)CD
2
CD-
(CH3)CD3; these results, together with kinetic data, have been rationalized
by a mechanism involving alkene insertion into a metal-alkyl bondY69l
There are, however, few unambiguous examples of such a mechanism and
this has led to alternative mechanisms being proposed. For example, it has
been argued that the [Ta(But)(C2H4h(PMe3h]-catalyzed dimerization of
L
1/11
Bu'-Ta
I "II
L
t
+C,H,

-L
Scheme 8
""'-TO "",jA)
I "II I "II
L L
+C,H,
t
-butlene
374
ethene to but-l-ene proceeds via a tantalcyclopentane intermediate
(Scheme 8).(17oa)
In contrast, the [Ta(CHBut)H(PMe3hI2]-catalyzed polymerization of
ethene is believed to proceed via a mechanism involving a tantalacyclo-
butane as outlined in Scheme 9. Strong support for this mechanism rather
than one involving alkene insertion into the metal-alkyl bond comes from
the detection of the intermediates (19, n = 0-4) by nmr when ethene-d
4
is used.(!70b)
H
I ,
[Taj=CHBu
-;-C,D,
----?
Scheme 9
H
I Bu'

D++D
D D
D D
1
I InC,D, I
[Taj=CD(C2D4)nCD2CH2Bu' [Taj=CDCD
2
CH
2
Bu'
19
Dynamic 13C nmr spectroscopy has been used to obtain kinetic and
thermodynamic data for the intermediate formed in the Ziegler catalyst
[TiCp2(Et)Cl] + AlEtCh. (171) It has been argued that homogeneous
analogs of the Philips (Cr03/Si02) and Union Carbide (chromocene/Si0
2
)
polyethylene catalysts should consist of coordinatively unsaturated dinu-
clear species since such species appear to be involved in the surface
reactions. i172i Kinetic studies of the polymerization of butadiene by
{[MO(1/3_C3H5)4] + CH
2
=CHCH
2
I + H
2
0}(!73) and the cotrimerization of
butadiene with styrene by [Ni(acach] + AIEt3 + PPh
3
(174) have been repor-
ted. The catalytic intermediate [Ni{1/3-MeCHC(Me)CHMe}cod]PF6 has
been isolated from the oligomerization reaction of ethene with [Ni( 1/3 -
MeC
3
H
4
)cod]PF
6
. (175) Isoprene undergoes cyclodimerization in the pres-
ence of [Ni(acach] + AlEt3 + PR
3
; the product distribution depends upon
the electronic properties of the ligand PR
3
since this changes the HOMO-
LUMO interactions between the nickel and the olefin. Strong 1T-acid PR
3
ligands promote head-to-head coupling and the formation of substituted
cyclohexenes.(176) The influence of aprotic solvents on the {[NiCh(PPh
3
h] +
NaBH
4
}-catalyzed oligomerization of isoprene has also been investi-
14.7 Oligomerization and Polymerization of Alkenes and Alkynes 375
gated.
l177l
Nuclear magnetic resonance and electron spin resonance studies
indicate that a tetrahedral or octahedral paramagnetic Ni(II) complex is
the active catalyst in the polymerization of CH
2
=C=CH
2
by [Ni(acachJ-
AIBU3. (178)
14.7.2. Reactions of Alkynes
The fact that the f..L -alkylidene complex [(CO)s-
W(f..L -CHCH b CMe2)W(CO)4] (20a) polymerizes terminal alkynes, that
in the case of but-2-yne the first insertion product of the monomer (20b)
has the same framework as (20a) around the metal centers and that this
intermediate reacts with alkynes to give the same polymers as complex
(20a) supports the mechanism outlined in Scheme 10 for the polymeriz-
ation of alkynes around two metal centers.(179) [Rh(CO)z(PPh
3
hh and
Scheme 10
R
R
0r
R
[Wl-[Wl
/\ RC=CR
[W]-[W] [Wl-[W]
1
R -
R;::
R R

[w]-[w]
1
RC
-('R Rt
[Wl-[Wl
R
R -
x<
R
R RC=CR

R - R R
[Wl-[Wl [Wl-[Wl
20b
[(PdCI)z(f..L Ph
2
PPh
2
)ZJ both catalyze the cyclotrimerization of
Me02CC CC0
2
Me and insight into the mechanisms comes from the
isolation of [Rh(COh{C
4
(C0
2
Me)4Rh(COh(PPh
3
)] (!80) and [(PdCI)z(f..L-
Ph
2
PCH
2
PPh
2
){f..L -C
2
( C0
2
Me)z}] (181) from the respective reactions.
14.8. Reactions of Dinitrogen
A review entitled "Mimicking Nitrogenase" has been published(182)
although the chemical systems studied to date are still far removed from
a viable homogeneous catalyst capable of fixing atmospheric nitrogen under
ambient conditions. Progress is, however, being made and a plausible
pathway for the electrochemical reduction of dinitrogen to an organo-
hydrazine is outlined in Scheme 11; each step in the cycle is based on
known chemistry. (183)
Scheme 11
+N,
-H,NNR,
[M(NNR
2
)(dpejzXr
2e. -x-
[M(N
2
)(N
2
R
2
)(dpelzl [M(NNR
2
)(dpe)zl

+N,
M = Mo or W; R = alkyl; X = Br or I
A kinetic study indicates that the proton at ion of trans-
[M(N2h(R2PCH2CH2PR2hJ (M = Mo or W, R = Et or Ph) with acids
HX (X = CI, Br, or HS0
4
) proceeds by rapid adduct formation between
the complex and HX, followed by the protonation of a coordinated
dinitrogen by another molecule of acid and then the rate-limiting dissoci-
ation of dinitrogen to yield finally the corresponding hydrazido(2-) complex
trans-[M(NNH2)X(R2PCH2CH2PR2hJY84a) The roles of protic solvents in
such protonations have been discussedY84b)
References
References for Chapter 1
1. C. Willis, J. Chern. Ed. 58, 88 (1981).
2. P. Neta, J. Chern. Ed. 58, 110 (1981).
3. M. Z. Hoffman and K. D. Whitburn, J. Chern. Ed. 58, 119 (1981).
4. R. M. Sellers, J. Chern. Ed. 58, 114 (1981).
5. Chern. Eng. News 59, 30, 38 (July 27, 1981).
6. L. Eberson, Adv. Phys. Org. Chern. 18,79 (1982).
7. M. Chan on and M. L. Tobe, Angew. Chern. Int. Ed. 21, 1 (1982).
8. E. D. German and A. M. Kuznetsov, Electrochirn. Acta 26, 1595 (1981).
9. B. L. Tembe, H. L. Friedman, and M. D. Newton, J. Chern. Phys. 76, 1490 (1982).
10. R. A. Marcus, J. Chern. Phys. 24, 966 (1955); 43,679 (1965).
11. R. D. Cannon, Chern. Phys. Lett. 49, 299 (1977).
12. A. P. Szecsy and A. Haim, J. Arn. Chern. Soc. 103, 1679 (1981).
13. M-S. Chan and A. C. Wahl, J. Phys. Chern. 86, 126 (1982).
14. S. Sahami and M. J. Weaver, J. Electroanal. Chern. 124, 35 (1981).
15. M. A. Ratner and R. D. Levine, J. Arn. Chern. Soc. 102,4898 (1980).
16. R. D. Cannon, Adv. Inorg. Chern. Radiochern. 21,179 (1978).
17. K. W. Frese, J. Phys. Chern. 85, 3911 (1981).
18. W. F. Prow, S. K. Garmestani, and R. D. Farina, Inorg. Chern. 20, 1297 (1981).
19. R. D. Farina, Inorg. Chern. 20,1331 (1981).
20. J. F. Endicott, B. Durham, and K. Kumar, Inorg. Chern. 21, 2437 (1982).
21. F. Scandola, V. Balzani, and G. B. Schuster, J. Arn. Chern. Soc. 103,2519 (1981).
22. R. J. Klingler and J. K. Kochi, J. Arn. Chern. Soc. 103, 5839 (1981).
23. M. Kimura, S. Yamabe, and T. Minato, Bull. Chern. Soc. Japan 54, 1699 (1981).
24. J. F. Endicott, B. Durham, M. D. Glick, T. J. Anderson, J. M. Kuszaj, W. G. Schmonsees,
and K. P. Balakrishman, J. Arn. Chern. Soc. 103, 1431 (1981).
25. M. Redi and J. J. Hopfield, J. Chern. Phys. 72, 6651 (1980).
26. L. J. Root and M. J. Ondrechen, Chern. Phys. Lett. 88, 538 (1982).
27. A. M. Kuznetsov and J. Ulstrup, J. Chern. Phys. 75, 2047 (1981).
28. S. Larsson, J. Arn. Chern. Soc. 103, 4034 (1981).
29. R. D. Cannon, Electron Transfer Reactions (Butterworths, Washington, D.C., 1980),
p.178.
377
378
References
30. S. K. S. Zawacky and H. Taube, 1. Am. Chern. Soc. 103, 3379 (1981).
31. B. S. Brunschwig, J. Logan, M. D. Newton, and N. Sutin, l. Am. Chern. Soc. 102, 5798
(1980).
32. M. D. Newton, Int. 1. Quantum Chern. Syrnp. 14, 363 (1980).
33. P. Siders and R. A. Marcus, 1. Am. Chern. Soc. 103,741 (1981).
34. E. Buhks, M. Bixon, and J. Jortner, 1. Phys. Chern. 85, 3759 (1981).
35. N. Sutin, Ann. Rev. Nucl. Sci. 12, 285 (1962).
36. T. K. Sham, J. B. Hastings, and M. L. Perlman, 1. Am. Chern. Soc. 102, 5904 (1980).
37. T. K. Sham and B. S. Brunschwig, l. Am. Chern. Soc. 103, 1590 (1981).
38. E. Buhks, M. Bixon, J. Jortner, and G. Navon, 1. Phys. Chern. 85, 3763 (1981).
39. D. Rehm and A. Weller, Ber. Bunsenges. Phys. Chern. 73, 834 (1969); Isr. 1. Chern. 8,
259 (1970).
40. R. A. Marcus, 1. Phys. Chern. 72, 891 (1968).
41. N. Agmon and R. D. Levine, Chern. Phys. Lett. 52, 197 (1977); see also Ref. 52, note
9.
42. E. Vogelmann, W. Rauscher, R. Traber, and H. E. A. Kramer, Z. phys. Chern.
(Frankfurt) 124, 13 (1981).
43. A. Kira, 1. Phys. Chern. 85, 3047 (1981).
44. A. Namiki, Y. Ito, and T. Higashimura, Chern. Phys. Lett. 88, 492 (1982).
45. V. Balzani, F. Scandola, G. Orlandi, N. Sabbatini, and M. T. Indelli, 1. Am. Chern.
Soc. 103, 3370 (1981).
46. N. Sabbatini, A. Golinelli, M. T. Gandolfi, and M. T. Indelli, Inorg. Chirn. Acta. 53,
L213 (1981).
47. C. Creutz, A. D. Keller, N. Sutin, and A. P. Zipp,l. Am. Chern. Soc. 104,3618 (1982).
48. C. Creutz and N. Sutin, 1. Am. Chern. Soc. 99, 241 (1977).
49. B. Brunschwig and N. Sutin, 1. Am. Chern. Soc. 100, 7568 (1978).
50. P. Siders and R. A. Marcus, 1. Am. Chern. Soc. 103,748 (1981).
51. R. A. Marcus and P. Siders, 1. Phys. Chern. 86, 622 (1982).
52. R. A. Marcus, Int. 1. Chern. Kinet. 13, 865 (1981).
53. L. A. A. de Oliveira and A. Haim, 1. Am. Chern. Soc. 104, 3363 (1982).
54. A. Vogler and J. Kisslinger, l. Am. Chern. Soc. 104, 2311 (1982).
55. A. Vogler and J. Kisslinger, Angew. Chern. Int. Ed. Eng. 21, 77 (1982).
56. W. Rybak, A. Haim, T. L. Netzel, and N. Sutin, 1. Phys. Chern. 85, 2856 (1981).
57. J. C. Curtis, J. S. Bernstein, R. H. Schmehl, and T. J. Meyer, Chern. Phys. Lett. 81,48
(1981).
58. T. J. Meyer, Chern. Phys. Lett. 64, 417 (1979).
59. P. Delahay, Chern. Phys. Lett. 87, 607 (1982).
60. P. Delahay, Acc. Chern. Res. 15,40 (1982).
61. R. D. Cannon, Adv. Inorg, Chern. Radiochern. 21, 179 (1978), see especially p. 219.
62. K. Y. Wong and P. N. Schatz, Prog. Inorg. Chern. 28, 369 (1981).
63. J. Lindenberg and M. A. Ratner,l. Am. Chern. Soc. 103, 3265 (1981).
64. C. Creutz and H. Taube, 1. Am. Chern. Soc. 91,3988 (1969); 95, 1086 (1973).
65. M. B. Robin and P. Day, Adv. Inorg. Chern. Radiochern. 10, 247 (1967).
66. E. Krausz, C. Burton, and J. Broomhead, Inorg. Chern. 20, 434 (1981).
67. M. E. Gress, C. Creutz, and C. O. Quicksall, Inorg. Chern. 20,1522 (1981).
68. M. Tanner and A. Ludi, Inorg. Chern. 20, 2348 (1981).
69. J. E. Sutton and H. Taube, Inorg. Chern. 20, 3125 (1981).
69a.J. E. Sutton, H. Krentzien, and H. Taube, Inorg. Chern. 21, 2842 (1982).
70. R. R. Gagne, C. L. Spiro, T. J. Smith, C. A. Hamann, W. R. Thies, and A. K. Shiemke,
1. Am. Chern. Soc. 103,4073 (1981).
References for Chapter 1 379
71. A. H. Tinnemans, K. Timmer, M. Reinten, J. G. Kraaijkamp, A. H. Alberts, J. G. M.
van der Linden, J. E. J. Schmitz, and A. A. Saaman, Inorg. Chem. 20, 3698 (1981).
72. R. D. Cannon, Electron Transfer Reactions (Butterworths, Washington, D.C., 1980),
p.136.
73. D. P. Rillema, R. W. Callahan, and K. B. Mack, Inorg. Chem. 21, 2589 (1982).
74. P. K. Mascharak, G. C. Papaefthymiou, R. B. Frankel, and R. H. Holm, I. Am. Chem.
Soc. 103, 6110 (1981).
75. P. J. Geary and D. P. E. Dickson, Biochem. 1.195, 199 (1981).
76. J. Watanabe, T. Saji, and S. Aoyagui, I. Electroanal Chem. 129, 369 (1981), and
references cited therein.
77. J. R. Ferraro and K. B. Mertes, Coord. Chem. Rev. 36, (1981).
78. D. R. Rosseinsky, J. A. Stephan, and J. S. Tonge, I. Chem. Soc. Faraday Trans. 1 77,
1719 (1981).
79. B. C. Bunker, M. K. Kroeger, R. M. Richman, and R. S. Drago, I. Am. Chem. Soc.
103,4254 (1981).
80. N. Gharbi, C. Sanchez, J. Livage, J. Lemerle, L. Nejem, and J. Lefebvre, Inorg. Chem.
21, 2758 (1982).
81. s. P. Harmalker and M. T. Pope, I. Am. Chem. Soc. 103,7381 (1981).
82. M. K. Johnson, R. D. Cannon, and D. B. Powell, Spectrochim. Acta 38A, 307 (1982).
83. C. T. Dziobkowski, J. T. Wroblewski, and D. B. Brown, Inorg. Chem. 20, 679 (1981).
84. H. W. Clark and B. I. Swanson, I. Am. Chem. Soc. 103,2928 (1981).
85. R. E. Hester and E. M. Nour, I. Chem. Soc., Dalton Trans., 939 (1981).
86. R. J. H. Clark and M. Kurmoo, Inorg. Chim. Acta 51,85 (1981).
87. R. J. H. Clark and M. Kurmoo, I. Chem. Soc., Dalton Trans., 524 (1981).
88. J. A. Koningstein, Ann. Rev. Phys. Chem. 24, 121 (1973); and see further, Refs. cited
in Ref. 89.
89. R. J. H. Clark and T. J. Dines, Mol. Phys. 45, 1153 (1982), and references cited therein.
90. K. Y. Wong and P. N. Schatz, Chem. Phys. Lett. 80,172 (1981).
91. K. Y. Wong and P. N. Schatz, Chem. Phys. Lett. 73, 456 (1980).
92. S. E. Butler, Phys. Rev. A. 23, 1 (1981).
93. J. N. Bardsley, Charge exchange and ionization in ion-atom collisions, in Atomic and
Molecular Collision Theory, F. A. Gianturco, ed. (NATO Advanced Study Institutes
Series, B, Vol. 71) (Plenum Press, New York, 1981).
94. R. B. Bernstein, Atom Molecule Collision Theory. A Guide for the Experimentalist
(Plenum Press, New York, 1979).
95. J. A. Jafri, J. Logan, and M. D. Newton, Isr. 1. Chem 19, 340 (1980).
96. J. K. Beattie and C. J. Moore, Inorg. Chem. 21,1292 (1982).
97. J. V. Dagdigian, V. McKee, and C. A. Reed, Inorg. Chem. 21,1332 (1982).
98. W. Siebrand, in The Triplet State, A. B. Zahlan, ed. (Cambridge University Press,
London, 1967), p. 31.
99. K. Funabashi, I. Chem. Phys. 76, 5519 (1982).
100. A. Bino, S. Cohen, and C. Heitner-Wirguin, Inorg. Chem. 21, 429 (1982).
101. F. A. Cotton and W. Wang, Inorg. Chem. 21, 2675 (1982).
102. H. J. Keller, B. Keppler, G. Ledezma-Sanchez, and W. Steiger, Acta Cryst. B 37,
674 (1981).
103. D. Datta, P. K. Mascharak, and A. Chakravorty, Inorg. Chem. 20, 1673 (1981).
104. D. Datta and A. Chakravorty, Inorg. Chem. 21, 363 (1982).
105. J. Martinsen, L. J. Pace, T. E. Phillips, B. M. Hoffmann, and J. A. Ibers, I. Am. Chem.
Soc. 104, 83 (1982).
106. L. Atkinson and P. Day, I. Chem. Soc. A, 2423 (1969).
380
References
107. C. Creutz, P. Kroger, T. Matsubara, T. L. Netzel, and N. Sutin, 1. Arn. Chern. Soc. 101,
5442 (1979).
108. A. J. Miralles, A. P. Szecsy, and A. Haim, Inorg. Chern. 21, 697 (1982).
109. J. C. Curtis and T. J. Meyer, Inorg. Chern. 21, 1562 (1982).
110. A. K. Viswanath, W. L. Smith, and H. H. Patterson, Chern. Phys. Lett. 87, 612 (1982).
111. M. Albin and H. H. Patterson, Chern. Phys. Lett. 73, 451 (1980).
112. R. H. Austin and J. J. Hopfield (cited Ref. 25, note 6).
113. J. C. Curtis, B. P. Sullivan, and T. J. Meyer, Inorg. Chern. 19, 3833 (1980).
114. D. Sedney and A. Ludi, Inorg. Chirn. Acta 47, 153 (1981).
115. K. K. Cloninger and R. W. Callahan, Inorg. Chern. 20, 1611 (1981).
116. N. Dowling, P. M. Henry, N. A. Lewis, and H. Taube, Inorg. Chern. 20, 2345 (1981).
1. R. Iadevia and J. E. Earley, Inorg. Chirn. Acta 53, L143 (1981).
2. S. Zakir-Ali, P. Chalilpayil, and J. E. Earley, Inorg. Chirn. Acta 48, 57 (1981).
3. R. N. Bose and J. E. Earley, Inorg. Chern. 20, 2739 (1981).
4. F. J. Kristine and R. E. Shepherd, Inorg. Chern. 20, 215 (1981).
5. R. A. Lee and J. E. Earley, Inorg. Chern. 20, 1739 (1981).
6. O. Olubuyide and J. E. Earley, Inorg. Chern. 20, 3569 (1981).
7. c.-K. Poon, T.-W. Tang, and T.-C. Lau, 1. Chern. Soc., Dalton Trans., 2556 (1981).
8. c.-K. Poon, T.-W. Tang, and T.-c. Lau, 1. Chern. Soc., Dalton Trans., 865 (1982).
9. W. C. Kupferschmidt and R. B. Jordan, Inorg. Chern. 20, 3469 (1981).
10. R. Bembi and O. P. Tandan, 1. Inorg. Nuclear Chern. 43, 309 (1981).
11. R. D. Williams, D. E. Pennington, and W. B. Smith, Inorg. Chirn. Acta 58, 45 (1982).
12. W. U. Malik, R. Bembi, and Sushi la, 1. Inorg. Nucl. Chern. 39, 345 (1977).
13. H. Ogino, E. Kikkawa, M. Shimura, and N. Tanaka, 1. Chern. Soc., Dalton Trans., 894
(1981).
14. P. B. Wood and W. C. E. Higginson, 1. Chern. Soc., 2116 (1965).
15. N. Serpone, M. A. Jamieson, S. S. Emmi, P. G. Fuochi, Q. A. Mulazzani, and M. Z.
Hoffman, 1. Arn. Chern. Soc. 103, 1091 (1981).
16. G. L. Robbins and R. E. Tapscott, inorg. Chern. 20, 2343 (1981).
17. A. Bakac and J. H. Espeson, 1. Arn. Chern. Soc. 103,2721 (1981).
18. A. Bakac and J. H. Espenson, Inorg. Chern. 20,1621 (1981).
19. J. H. Espenson and A. Bakac, 1. Arn. Chern. Soc. 103,2728 (1981).
20. S. A. Chimatadar and J. R. Raju, 1. Inorg. Nucl. Chern. 43,1947 (1981).
21. M. K. Aronachalam, P. N. Balasubramanian, and V. R. Vijayaraghavan, 1. Inorg.
Nuclear Chern. 43, 753 (1981).
22. P. N. Balasubramanian and V. R. Vijayaraghavan, Inorg. Chirn. Acta 53, L209 (1981).
23. E. Pramauro, E. Pelizzetti, S. Diekmann, and 1. Frahm, inorg. Chern. 21, 2432 (1982).
24. R. van Eldik and H. Keirn, inorg. Chirn. Acta 60, 177 (1982).
25. L. Spiccia and D. W. Watts, Aust. 1. Chern. 32, 2275 (1979).
26. R. van Eldik, Inorg. Chern. 21, 2501 (1982).
27. K. Shigehera, N. Oyama, and F. C. Anson, Inorg. Chern. 20, 518 (1981).
28. T. Ikeda, C. R. Leidner, and R. W. Murray, 1. Arn. Chern. Soc. 103, 7422 (1981).
29. A. J. Miralles, A. P. Szecsy, and A. Haim, Inorg. Chern. 21, 697 (1982).
30. H. Cohen, M. Nutkovich, D. Meyerstein, and K. Weighardt, 1. Chern. Soc., Dalton
Trans., 943 (1982).
31. J. C. Curtis and T. J. Meyer, Inorg. Chern. 21,1562 (1982).
32. A. P. Szecsy and A. Haim, J. Am. Chem. Soc. 103, 1679 (1981).
33. A. P. Szecsy and A. Haim, J. Am. Chem. Soc. 104, 3063 (1982).
34. W. Rybak, A. Haim, T. L. Netzel, and N. Sutin, J. Phys. Chem. 85, 2856 (1981).
35. L. A. A. de Oliveira and A. Haim, 1. Am. Chem. Soc. 104, 3363 (1982).
36. E. Pelizzetti and R. Giordano, J. Inorg. Nucl. Chem. 43, 2463 (1981).
37. D. Burchardt, K. Pool, and S. Wherland, Inorg. Chem. 21, 93 (1982).
38. J. R. Pladziewicz and M. T. Carney, J. Am. Chem. Soc. 104, 3544 (1982).
39. T. T.-T. Li, M. J. Weaver, and C. H. Brubaker, J. Am. Chem. Soc. 104,2381 (1982).
40. J. F. Endicott, B. Durham, and K. Kumar, Inorg. Chem. 21, 2437 (1982).
41. B. T. Reagor and D. H. Huchital, Inorg. Chem. 21, 703 (1982).
42. c.-L. Wong and J. F. Endicott, Inorg. Chem. 20, 2233 (1981).
43. J. F. Endicott, B. Durham, M. D. Glick, T. 1. Anderson, J. M. Kuszaj, W. A. Schmonsees,
and K. P. Balasubramanian, 1. Am. Chem. Soc. 103, 1431 (1981).
44. R. D. Chapman and E. B. Fleischer, J. Chem. Soc., Chem. Commun., 332 (1981).
45. R. D. Chapman and E. B. Fleischer, J. Am. Chem. Soc. 104, 1575 (1982).
46. R. D. Chapman and E. B. Fleischer, J. Am. Chem. Soc. 104, 1582 (1982).
47. W. H. Tamblyn, R. J. Klingler, W. S. Hwang, and J. K. Kochi, J. Am. Chem. Soc. 103,
3161 (1981).
48. V. S. Srinivasan and E. S. Gould, Inorg. Chem. 20, 208 (1981).
49. Y. T. Fanchiang, Inorg. Chem. 21, 2344 (1982).
50. J. C. Brodovitch and A. McAuley, Inorg. Chem. 20, 1667 (1981).
51. E. Zeigerson, I. Bar, J. Bernstein, L. J. Krischenbaum, and D. Meyerstein, Inorg. Chem.
21,73 (1982).
52. P. Morliere and L. K. Paterson, Inorg. Chem. 20, 1458 (1981).
53. P. Morliere and L. K. Paterson, Inorg. Chem. 21, 1837 (1982).
54. P. Morliere and L. K. Patterson, Inorg. Chem. 21, 1833 (1982).
55. S. N. Bhattacharyya and P. Neta, J. Phys. Chem. 85, 1527 (1981).
56. S. N. Bhattacharyya, N. C. Saha, and P. Neta, J. Phys. Chem. 85, 300 (1981).
57. A. Bencini, L. Fabbrizzi, and A. Poggi, Inorg. Chem. 20, 2544 (1981).
58. 1. C. Brodovitch, R. I. Haines, and A. McAuley, Can. J. Chem. 59, 1610 (1981).
59. H. M. Khan, W. L. Waltz, J. LiIie, and R. I. Woods, Inorg. Chem. 21,1489 (1982).
60. N. AI-Shatti, A. G. Lappin, and A. G. Sykes, Inorg. Chem. 20,1466 (1981).
61. P. Leupin, N. AI-Shatti, and A. G. Sykes, J. Chem. Soc., Dalton Trans., 927 (1982).
62. M. Freiberg, D. Meyerstein, and Y. Yamamoto, J. Chem. Soc., Dalton Trans., 1137
(1982).
63. M. A. Augustin, I. K. Yandell, A. W. Addison, and K. D. Karlin, Inorg. Chim. Acta
55, L35 (1981).
64. I. K. Yandell, Aust. 1. Chem. 34, 99 (1981).
65. M. A. Augustin and J.K. Yandell, Aust. J. Chem. 34, 91 (1981).
66. B. T. Ahn and D. R. McMillin, Inorg. Chem. 20, 1427 (1981).
67. c. A. Koval and D. W. Margerum, Inorg. Chem. 20, 2311 (1981).
68. G. D. Owens and D. W. Margerum, Inorg. Chem. 20,1446 (1981).
69. I. S. Rybka and D. W. Margerum, Inorg. Chem. 20, 1453 (1981).
70. M. A. Harmer, D. T. Richens, A. B. Soares, A. T. Thornton, and A. G. Sykes, Inorg.
Chem. 20, 4155 (1981).
71. S. Kondo, Y. Sasaki, and K. Saito, Inorg. Chem. 20, 429 (1981).
72. S.-I. Miyake, K. Tanaka, and T. Tanaka, J. Chem. Soc., Dalton Trans., 292 (1981).
73. B. A. Moyer and T. J. Meyer, Inorg. Chem. 20,436 (1981).
74. R. A. Binstead, B. A. Moyer, G. J. Samuels, and T. J. Meyer, 1. Am. Chem. Soc. 103,
2897 (1981).
382 References
75. J. F. Ojo, A. O. OJ odium, and O. A. Olubuyide,J. Chern. Soc., Dalton Trans., 659 (1982).
76. J. Ige, J. F. Ojo, and O. Olubuyide, Inorg. Chern. 20,1757 (1981).
77. M. S. Cham and A. C. Wahl, 1. Phys. Chern. 86,126 (1982).
78. M. E. Gress, C. Creutz, and C. o. Quicksell, Inorg. Chern. 20, 1522 (1981).
79. S. K. S. Zawacky and H. Taube, 1. Arn. Chern. Soc. 103,3379 (1981).
80. C. A. Stein, N. A. Lewis, and G. Seitz, 1. Arn. Chern. Soc. 104, 2596 (1982).
81. K. Chandrasekaran and P. Natarajan, 1. Chern. Soc., Dalton Trans., 478 (1981).
82. G. McLendon and W. F. Mooney, Inorg. Chern. 19, 12 (1980).
83. K. Krist and H. D. Gafney, 1. Phys. Chern. 86, 951 (1982).
84. K. Leopold and A. Haim, Inorg. Chern. 17, 1753 (1978).
85. W. Bottcher and A. Haim, Inorg. Chern. 21, 531 (1982).
86. c. V. Krishnan and N. Sutin, 1. Arn. Chern. Soc. 103, 2141 (1981).
87. S.-F. Chan, M. Chou, C. Creutz, T. Matsubara, and N. Sutin, 1. Arn. Chern. Soc. 103,
369 (1981).
88. Q. G. Mulzzani, S. Emmi, M. Z. Hoffman, and M. Venturi, 1. Arn. Chern. Soc. 103,
3362 (1981).
89. Q. G. Mulzzani, M. Ventori, and M. Z. Hoffman, 1. Phys. Chern. 86, 242 (1982).
90. C. Creutz, A. D. Keller, N. Sutin, and A. P. Zipp, 1. Am. Chern. Soc. 104, 3618 (1982).
91. A. Vogle and J. Kisslinger, 1. Am. Chern. Soc. 104,2311 (1982).
92. P-A Brugger, P. P. Infelta, A. M. Braun, and M. Gratzel, 1. Am. Chern. Soc. 103, 320
(1981).
93. M. S. Tunuli and J. H. Fendler, 1. Am. Chern. Soc. 103, 2507 (1981).
94. P. A. Brugger, P. Cuendet, and M. Gratzel, 1. Am. Chern. Soc. 103, 2923 (1981).
95. D. Duonghoug, E. Bargarello, and M. Gratzel, 1. Am. Chern. Soc. 103,4685 (1981).
96. D. S. Miller and G. McLendon, 1. Am. Chern. Soc. 103,6791 (1981).
97. E. Borgarello, J. Kiwi, M. Gratzel, E. Pelizzetti, and M. Visca,l. Am. Chern. Soc. 104,
2996 (1982).
98. D. Duonghong, J. Ramsden, and M. Gratzel, 1. Am. Chern. Soc. 104, 2977 (1982).
99. T. Matusinovic and D. E. Smith, Inorg. Chern. 20, 3121 (1981).
100. V. S. Srinivasan, C. A. Radlowski, and E. S. Gould, Inorg. Chern. 20, 2094 (1981).
101. V. S. Srinivasan, A. N. Singh, C. A. Radlowski, and E. S. Gould, Inorg. Chern. 21,
1240 (1982).
102. P. K. Sidem, A. W. Maverick, and H. B. Gray, Inorg. Chirn. Acta 50,59 (1981).
103. A. W. Maverick and H. B. Gray, 1. Am. Chern. Soc. 103, 1298 (1981).
104. D. G. Nocera and H. B. Gray, 1. Am. Chern. Soc. 103,7349 (1981).
105. C-M Che, L. G. Butler, and H. B. Gray, 1. Am. Chern. Soc. 103, 7796 (1981).
106. W. J. Albery, M. J. Eddowes, H. A. O. Hill, and A. R. Hillman, 1. Am. Chern. Soc.
103,3904 (1981).
107. D. Cummins and H. B. Gray, Inorg. Chern. 20, 3711 (1981).
108. B. S. Brunschwig and N. Sutin, Inorg. Chern. 115, 631 (1976).
109. J. Butler, D. M. Davies, and A. G. Sykes, 1. Inorg. Biochern. 15,41 (1981).
110. J. Butler, D. M. Davies, A. G. Sykes, W. H. Koppenol, N. Osheroff, and E. Margoliash,
1. Am. Chern. Soc. 63, 469 (1981).
111. G. McLendon and M. Smith, Inorg. Chern. 21, 847 (1982).
112. L. S. Reid and A. G. Mauk, 1. Am. Chern. Soc. 104, 841 (1982).
113. S. A. Schichman and H. B. Gray, 1. Am. Chern. Soc. 103, 7794 (1981).
114. 1. K. Adzamli, H. o. A. Kim, A. G. Sykes, and G. V. Buxton, 1. Inorg. Biochern. 16,
311 (1982).
115. I. K. Adzamli, D. M. Davies, C. S. Stanley, and A. G. Sykes, 1. Am. Chern. Soc. 103,
5543 (1981).
383
116. G. Aprahamian and B. A. Feinberg, Biochernistry 20,915 (1981).
117. A. M. English, V. R. Lum, P. J. DeLaive, and H. B. Gray, J. Arn. Chern. Soc. 104,
870 (1982).
118. O. Farver and L. Pecht, Isr. J. Chern. 21, 13 (1981).
1. B. Banas, Inorg. Chirn. Acta 53, L13 (1981).
2. A. G. Lappin, M. C. M. Laranjeira, and L. Youde-Owei, J. Chern. Soc., Dalton Trans.,
721 (1981).
3. K. Tsukahara and Y. Yamamoto, Bull. Chern. Soc. Japan 54,2642 (1981).
4. K. Tsukahara, T. Izumitani, and Y. Yamamoto, Bull. Chern. Soc. Japan 55, 130 (1982).
5. M. Kimura, M. Yamamoto, and S. Yamabe, J. Chern. Soc., Dalton Trans., 423 (1982).
6. C. Creutz, Inorg. Chern. 20, 4449 (1981).
7. S. Steenken and P. Neta, J. Phys. Chern. 83, 1134 (1979).
8. B. H. J. Bielski, A. O. Allen, and H. A. Schwarz, J. Arn. Chern. Soc. 103, 3516 (1981).
9. R. F. Jameson and N. J. Blackburn, J. Chern. Soc., Dalton Trans., 9 (1982).
12. c. V. Krishnan and N. Sutin, J. Arn. Chern. Soc. 103, 2141 (1981).
13. R. A. Holwerda and M. L. Ettel, Inorg. Chern. 21, 830 (1982).
14. R. A. Holwerda, Inorg. Chern. 21, 2107 (1982).
15. N. Al-Shatti, A. G. Lappin, and A. G. Sykes, Inorg. Chern. 20, 1466 (1981).
16. E. Pelizetti and E. Mentasti, Z. Phys. Chern. 105,21 (1977).
17. M. Kimura, S. Yamabe, and T. Minatu, Bull. Chern. Soc. Japan 54, 1699 (1981).
18. S. Yamabe, T. Minato, and M. Kimura, J. Phys. Chern. 85, 3510 (1981).
19. M. D. Stallings, M. M. Morrison, and D. T. Sawyer, Inorg. Chern. 20, 2655 (1981).
20. S. E. Jones, D.-H. Chin, and D. T. Sawyer, Inorg. Chern. 20,4257 (1981).
21. R. B. Lauffer, R. H. Heistand, and L. Que, J. Arn. Chern. Soc. 103,3947 (1981).
22. R. H. Heistand, R. B. Lauffer, E. Fikrig, and L. Que, 1. Arn. Chern. Soc. 104, 2289
(1982).
23. J. M. T. Raycheba and D. W. Margerum, Inorg. Chern. 20, 45 (1981).
24. J. M. T. Raycheba and D. W. Margerum, Inorg. Chern. 20,1441 (1981).
25. G. Nord, B. Pedersen, E. Floryan-Lovberg, and P. Pagsberg, Inorg. Chern. 21, 2327
(1982).
26. L. I. Elding and L. F. Olsson, Inorg. Chern. 21, 779 (1982).
27. L. I. Elding, A. B. Groning, and O. Groning, J. Chern. Soc., Dalton Trans., 1093 (1981).
27a. J. F. Glenister, K. E. Hyde, and G. Davies, Inorg. Chern. 21, 2331 (1982).
27b. R. D. Cannon, D. B. Powell, and K. Sarawek, Inorg. Chern. 20, 1470 (1981).
28. P. J. Morando, E. B. Barghi, L. M. De Schteingart, and M. A. Blesa, J. Chern. Soc.
Dalton Trans., 435 (1981).
29. H. Sakurai, S. Shimomura, and K. Ishizu, Inorg. Chirn. Acta 55, 667 (1981).
30. M. J. Roof, I. K. Adzamli, and E. Deutsch, Inorg. Chern. 20,4017 (1981).
31. H. N. Po, C.-F. Lo, N. K. Jones, A. A. Galuska, and H. Evan, J. Coord. Chern. 11,
163 (1981).
32. J. M. Anast and D. W. Margerum, Inorg. Chern. 20, 2319 (1981).
33. A. A. El-Awady and G. M. Harris, Inorg. Chern. 20,4251 (1981).
34. R. K. Pada, G. Neogi, and D. Ramaswamy, Int. J. Chern. Kinet. 13, 1001 (1981).
35. R. K. Pada, G. Neogi, and D. Ramaswamy, Bull. Chern. Soc. Japan 55, 587 (1982).
384 References
36. F. Cristiani, F. A. Devillanova, A. Diza, and G. Verani, Inorg. Chim. Acta 50, 251
(1981).
37. S. Surinivasan, R. Venkatasamy, and S. Rajagopal, Ind. 1. Chem. 20A, 505 (1981).
38. L. S. A. Dikshitulu, P. Vari, and V. H. Rao, J. Inorg. Nuclear Chem. 43, 1261 (1981).
39. L. S. A. Dikshitulu, V. H. Rao, and S. N. Dindi, Ind. J. Chm. 20A, 784 (1981).
40. M. J. Ridd and F. R. Keene, J. Am. Chem. Soc. 103, 5733 (1981).
41. T. J. Kemp, P. Moore, and G. R. Quick, J. Chem. Res. (S) 33 (M); 301 (1981).
42. V. S. Srinivasan and E. S. Gould, Inorg. Chem. 20, 3176 (1981).
43. A. K. Gupta, B. C. Joshi, and Y. K. Gupta, Ind. J. Chem. 20A, 276 (1981).
44. R. Balakrishnan, V. S. Srinivasan, and N. Venkatasubramanian, Ind. J. Chem. 20A,
476 (1981).
45. M. A. Rao, B. Sethuran, and T. N. Rao, Ind. J. Chem. 20A, 575 (1981).
46. F. Ahmad and V. S. Baswami, Int. 1. Chem. Kinet. 13, 565 (1981).
47. F. Freeman, C. O. Fuselier, C. R. Armisted, C. E. Dalta, P. A. Davidson, E. M.
Karchesfki, D. E. Krochman, M. N. Johnson, and N. K. Jones, 1. Am. Chem. Soc. 103,
1154 (1981).
48. H. N. Singh, E. Gelerinter, and E. S. Gould, Inorg. Chem. 21,1232 (1982).
49. N. H. Singh, V. S. Srinivasan, and E. S. Gould, Inorg. Chem. 21, 1236 (1982).
50. A. N. Singh, C. A. Radlowski; J. W. Reed, V. V. Krishnamurthy, and E. S. Gould, Inorg.
Chem. 20, 211 (1981).
51. V. S. Srinivasan, C. A. Radlowski, and E. S. Gould, Inorg. Chem. 20, 3172 (1981).
52. H. Boucher, A. M. Sargeson, D. F. Sangster, and J. C. Sullivan, Inorg. Chem. 20, 3719
(1981).
53. S. Ramesh, S. N. Mahapatro, J. H. Liu, and J. Rocek, J. Am. Chem. Soc. 103, 5172
(1981).
54. R. N. Mehrotra, J. Chem. Soc., Dalton Trans., 897 (1981).
55. B. Singh, B. B. Singh, and R. P. Singh, I. Inorg. Nuclear Chem. 43,1283 (1981).
56. G. Calvaruso, F. P. Cavasino, and C. Sbriziolo, Int. J. Chem. Kinet. 13, 135 (1981).
57. G. Calvaruso, F. P. Cavasino, and C. Sbriziolo, Int. J. Chem. Kinet. 13, 1029 (1981).
58. R. R. Nagori, M. Mehta, and R. N. Mehrotra, J. Inorg. Nucl. Chem. 43, 2899 (1981).
59. S. Prasad and R. K. Prasad, Ind. J. Chem. 20A, 181 (1981).
60. M. Yamaguchi, S. Yamamatsu, H. Oikawa, M. Saburi, and S. Yoshikawa, Inorg. Chem.
20,3179 (1981).
61. K. B. Reddy, B. Sethuram, and T. N. Rao, Ind. J. Chem. 20A, 395 (1981).
62. L. M. Bharadwaj and P. C. Nigan, Ind. J. Chem. 20A, 793 (1981).
63. J. S. Reckley and K. Showalker, J. Am. Chem. Soc. 103, 7012 (1981).
64. v. S. Singh, Ind. J. Chem. 20A, 734 (1981).
65. J. Konstantatos, E. Vrachnou-Astra, N. Katsaros, and D. Katakis, Inorg. Chem. 21,
122 (1982).
66. H. K. Mao and D. L. Leussing, Inorg. Chem. 20,4240 (1981).
67. M. Birus and D. L. Leussing, Inorg. Chem. 21, 374 (1982).
68. R. R. Nagori, M. Mehta, and R. N. Mehrotra, J. Chem. Soc., Dalton Trans., 581 (1981).
69. R. N. Nagori, M. Mehta, and R. N. Mehrotra, Ind. J. Chem. 21A, 41 (1982).
70. A. Kumar,l. Am. Chem. Soc. 103, 5179 (1981).
71. P.1. P. Rao, B. Sethuram, and T. N. Rao, Ind. J. Chem. 20A, 733 (1981).
72. K. B. Reddy, C. P. Murthy, B. Sethuram, and T. N. Rao, Ind. 1. Chem. 20A, 272 (1981).
73. K. K. Sen Gupta and V. Chatterjee, J. Inorg. Nucl. Chem. 43, 2491 (1981).
74. I. Bhatia and K. K. Banerji, J. Chem. Res. (5)97; (M) 1076 (1981).
75. S. Wolfe, C. F. Ingold, and R. U. Lemieux, J. Am. Chem. Soc. 103, 938 (1981).
76. S. Wolfe and C. F. Ingold, 1. Am. Chem. Soc. 103, 940 (1981).
385
77. S. Steenken and P. Neta, f. Am. Chern. Soc. 104, 1244 (1982).
78. R. L. Rollick and J. K. Kochi, f. Am. Chern. Soc. 104, 1319 (1982).
79. P. Natarajan and N. V. Raghavan, 1. Phys. Chern. 85, 188 (1981).
80. D. A. Ryan and J. H. Espenson, Inorg. Chern. 21, 527 (1982).
81. R. C. McHatton, 1. H. Espenson, and A. Bakac, 1. Am. Chern. Soc. 104, 3531 (1982).
82. R. A. Henderson, G. Davies, J. R. Dilworth and R. N. F. Thornley, f. Chern. Soc.,
83. S. N. Anderson, M. E. Farley, R. L. Richards, and J. Chatt, f. Chern. Soc., Dalton
Trans., 1973 (1981).
84. R. A. Henderson, f. Chern. Soc., Dalton Trans., 917 (1982).
85. G. N. Schrauzer and M. R. Palmer, f. Am. Chern. Soc. 103, 2659 (1981).
86. M. N. Hughes, M. Okolow-Zubkowska, and H. L. Wallis, f. Chern. Soc., Dalton Trans.,
2009 (1981).
87. K. A. Pearsall and F. T. Bonner, Inorg. Chern. 21,1978 (1982).
88. F. T. Bonner and K. A. Pearsall, Inorg. Chern. 21, 1973 (1982).
89. D. T. Doughty, R. P. Stewart, and G. Gordon, f. Am. Chern. Soc. 103, 3388 (1981).
90. I. R. Epstein, K. Kustin, and R. H. Simoyi, f. Am. Chern. Soc. 104,712 (1982).
91. L. S. A. Dikshitulu, G. Chandrasekharam, V. H. Rao, and P. Vani, f. Inorg. Nucl.
Chern. 43, 2455 (1981).
92. A. K. Indrayan, S. K. Mishra, and Y. K. Gupta, Inorg. Chern. 20, 450 (1981).
93. A. K. Indrayan, S. K. Mishra, and Y. K. Gupta, Inorg. Chern. 20,1924 (1981).
94. S. S. Gupta and Y. K. Gupta, Inorg. Chern. 20,1748 (1981).
95. S. S. Gupta and Y. K. Gupta, Inorg. Chern. 20, 454 (1981).
96. M. J. B1andamer, J. Burgess, N. V. Reed, and P. Wellings, f. Inorg. Nucl. Chern. 43,
3245 (1981).
97. V. C. Singh and K. Venkataro, Int. f. Chern. Kinet. 13, 555 (1981).
98. S. P. Srinvastava, V. K. Gupta, R. G. Sharma, and B. P. Singh, Ind. f. Chern. 20A,
1221 (1981).
99. A. S. Reddy and J. N. Reddy, Ind. f. Chern. 20A, 608 (1981).
100. D. Meyerstein, f. Inorg. Nucl. Chern. 43, 401 (1981).
101. S. C. Agarwal, G. Chandra, and S. K. Jha, 1. Inorg. Nucl. Chern. 41, 899 (1979).
102. R. C. Thompson, Inorg. Chern. 20, 1005 (1981).
105. R. C. Thompson and E. H. Appelman, Inorg. Chern. 20, 2114 (1981).
106. A. K. Indrayan, S. K. Mishra, and Y. K. Gupta, f. Chern. Soc., Dalton Trans., 549
(1982).
107. A. Y. Kassin and Y. Sulfab, Inorg. Chern. 20, 506 (1981).
108. A. A. Abdel-Khalek and Y. Sulfab, f. Inorg. Nucl. Chern. 43, 3257 (1981).
109. T. M. Vickrey and R. A. Kok, f. Inorg. Nucl. Chern. 43,1399 (1981).
110. P. Guardado, A. Maestre, and M. Balan, f. Inorg. Nucl. Chern. 43,1391 (1981).
111. P. S. Radhakrishnamurti and S. A. Misra, Ind. f. Chern. 20A, 797 (1981).
112. P. De Kepper, I. R. Epstein, and K. Kustin, f. Am. Chern. Soc. 103, 6121 (1981).
113. P. De Kepper, I. R. Epstein, and K. Kustin, f. Am. Chern. Soc. 103,2133 (1981).
114. K. Showalter, f. Phys. Chern. 85,440 (1981).
115. W. Geiseler and K. Bar-Eli, f. Phys. Chern. 85, 908 (1981).
116. S. D. Furrow and R. M. Noyes, f. Am. Chern. Soc. 104,38 (1982).
117. S. D. Furrow and R. M. Noyes, f. Am. Chern. Soc. 104,42 (1982).
118. R. M. Noyes and S. D. Furrow, f. Am. Chern. Soc. 104,45 (1982).
119. P. De Kepper and I. R. Epstein, f. Am. Chern. Soc. 104,49 (1982).
386 References
120. C. F. Dateo, M. Orban, P. De Kepper and I. R. Epstein, J. Arn. Chern. Soc. 104, 504
(1982).
121. P. S. Krishramurti and L. D. Sarange, Ind. J. Chern. 20A, 301 (1981).
122. A. H. Khan and W. C. E. Higginson, J. Chern. Soc., Dalton Trans., 2532 (1981).
123. D. A. Ryan and J. H. Espenson, J. Arn. Chern. Soc. 104, 704 (1982).
124. J. R. Budge, B. M. K. Gatehouse, M. C. Nesbit, and B. O. West, J. Chern. Soc., Chern.
Cornrnun., 370 (1981).
125. N. T. Moxon, P. E. Fielding, and A. K. Gregson, J. Chern. Soc., Chern. Cornrnun., 98
(1981).
126. W. M. Coleman and L. Taylor, Inorg. Chirn. Acta 61, 13 (1982).
127. T. Geiger and F. C. Anson, J. Arn. Chern. Soc. 103, 7489 (1981).
128. C. L. Wong, 1. A. Switzer, B. P. Balakrishnan, and 1. F. Endicott, J. Arn. Chern. Soc.
102,5511 (1980).
129. Y. Sasaki, K. Z. Suzuki, A. Matsumoto, and K. Saito, Inorg. Chern. 21,1825 (1982).
130. M. M. Taqui-Khan and G. Ramachadraiah, Inorg. Chern. 21, 2109 (1982).
131. A. Zombeck, R. S. Drago, B. D. Corden, and J. H. Gaul, J. Arn. Chern. Soc. 103,7580
(1981).
132. A. Nishinaga, H. Tomita, K. Nishigawa, T. Matsuura, S. Ooi, and K. Hirotsu, J. Chern.
Soc., Dalton Trans., 1504 (1981).
133. S. Bhaduri and N. Y. Sapne, J. Chern. Soc., Dalton Trans., 2585 (1981).
134. T. Salazar, R. Baraona, and W. Zamudio, J. Inorg. Nucl. Chern. 43, 2881 (1981).
135. M. Otto, 1. Lerchner, T. Pap, H. Zwanziger, E. Hoyer, J. Inczedy, and G. Werner,
J. Inorg. Nucl. Chern. 43,1101 (1981).
136. K. A. Reich, L. E. Marshall, D. R. Graham, and D. S. Sigman, J. Arn. Chern. Soc. 103,
3582 (1981).
137. G. M. Clive, M. R. Hollaway, C. Orengo, J. Peterson, and M. T. Wilson, Inorg. Chern.
Acta 56, 143 (1981).
138. L. Nagy, Z. M. Galbacs, L. 1. Csanyi, and L. Horvath, J. Chern. Soc., Dalton Trans.,
859 (1982).
139. E. N. Rizkalla, O. H. El-Shafey, and N. M. Guindy, Inorg. Chirn. Acta 57, 199 (1982).
140. P. Banerjee and M. P. Pujari, Bull. Chern. Soc. Japan 54,2496 (1981).
141. F. J. Kristine, R. E. Shepherd, and S. Siddiqui, Inorg. Chern. 20, 2571 (1981).
142. M. P. Heyward and C. F. Wells, J. Chern. Soc., Dalton Trans., 1863 (1981).
143. M. P. Heyward and C. F. Wells, J. Chern. Soc., Dalton Trans., 431 (1981).
144. C. Walling, K. Amornath, and C. B. Campbell, J. Arn. Chern. Soc. 104, 1185 (1982).
145. Y. Ogata and K. Tanaka, Can. J. Chern. 59, 718 (1981).
146. G. H. Jones, J. Chern. Res. (S), 228-229; (M), 2801 (1981).
147. B. A. Moyer, B. K. Supa, and T. J. Meyer, Inorg. Chern. 20, 1475 (1981).
148. G. M. Tietavainen and H. N. Po, Inorg. Chirn. Acta 52,35 (1981).
149. M. Bhattacharjee, A. K. Bhattacharjee, and M. K. Mahanti, Bull. Chern. Soc. Japan
54,3566 (1981).
150. M. B. Moorima and J. M. Pratt, J. Chern. Soc., Chern. Cornrnun., 33 (1981).
151. D. A. Ryan and J. H. Espenson, Inorg. Chern. 20,4401 (1981).
1. D. Rehorek, R. Herzschuh, and H. Hennig, Inorg. Chirn. Acta 44, L75 (1980).
2. M. P. Crozet and P. Tordo, Inorg. Chirn. Acta 53, L57 (1981).
387
3. M. Bhattacharjee, A. K. Bhattacharjee, and M. K. Mahanti, Bull. Chern. Soc. lpn. 54,
3566 (1981).
4. M. L. McKee and W. N. Lipscomb, Inorg. Chern. 20,4148 (1981).
5. H. Noth, R. Staudigl, and R. Briickner, Chern. Ber. 114, 1871 (1981).
6. H. Noth and R. Staudigl, Chern. Ber. 115, 1555 (1982).
7. C. Chatgilialoglu, K. U. Ingold, 1. C. Scaiano, and H. Woynar, l. Arn. Chern. Soc. 103,
3231 (1981).
8. K. P. Steele and W. P. Weber, Inorg. Chern. 20, 1302 (1981).
9. K. P. Steele, D. Tzeng, and W. P. Weber, l. Organornet. Chern. 231, 291 (1982).
10. C. Eaborn and F. M. S. Mahmoud, l. Organornet. Chern. 206, 49 (1981).
11. C. Eaborn and F. M. S. Mahmoud,!. Organornet. Chern. 209,13 (1981).
12. G. Seconi, C. Eaborn, and 1. G. Stamper, l. Organornet. Chern. 204, 153 (1981).
13. C. Eaborn and F. M. S. Mahmoud, l. Organornet. Chern. 205,47 (1981).
14. 1.-1. Tondeur, A. Borghese, and G. Vandenunghen, l. Chern. Res. (5), 134 (1981);
(M), 1628 (1981).
15. S. A. 1. AI-Shali, C. Eaborn, and F. M. S. Mahmoud, l. Organornet. Chern. 232, 215
(1982).
16. S. Kozuka, T. Higashino, and T. Kitamura, Bull. Chern. Soc. lpn. 54, 1420 (1981).
17. W. H. Stevenson and 1. C. Martin, l. Arn. Chern. Soc. 104,309 (1982).
18. W. B. Farnham and R. L. Harlow, l. Arn. Chern. Soc. 103,4608 (1981).
19. T. Ibaraki and K. Ito, Bull. Chern. Soc. lpn. 54, 3235 (1981).
20. E. C. Friedrich and G. De Lucca, l. Organornet. Chern. 226, 143 (1982).
21. R.I. P. Corriu and C. Guerin, l. Organornet. Chern. 225, 141 (1982).
22. D. D. Davis and H. M. lacocks, l. Organornet. Chern. 206, 33 (1981).
23. 1. B. Lambert and R. B. Finzel, l. Arn. Chern. Soc. 104,2020 (1982).
24. R. K. Harris, C. T. G. Knight, and W. E. Hull, l. Arn. Chern. Soc. 103, 1577 (1981).
25. G. Engelhardt, D. Hoebbel, M. Tarmak, A. Samsonov, and E. Lippmaa, Z. Anorg.
Allg. Chern. 484, 22 (1982).
26. J. Mason, Chern. Rev. 81, 205 (1981).
27. R. A. Kenley, P. L. Trevor, and B. Y. Lan, l. Arn. Chern. Soc. 103, 2203 (1981).
28. R. K. Broszkiewicz, E. Kozlowska-Milner, and A. Blum, l. Phys. Chern. 85, 2258 (1981).
29. R. B. Moodie, K. Schofield, P. G. Taylor, and P. J. Baillie, f. Chern. Soc., Perkin Trans.
2,842 (1981).
30. 1. Johansson and T. Olsson, Acta Chern. Scand. A35, 481 (1981).
31. L. Main, R. B. Moodie, and K. Schofield, l. Chern. Soc., Chern. Cornrnun., 48 (1982).
32. 1. C. Giffney and 1. H. Ridd, l. Chern. Soc., Perkin Trans. 2, 618 (1979).
33. F. AI-Omran, K. Fujiwara, 1. C. Giffney, J. H. Ridd, and S. R. Robinson, l. Chern.
Soc., Perkin Trans. 2, 519 (1981).
34. P. Helsby and J. H. Ridd, l. Chern. Soc., Chern. Cornrnun., 926 (1980).
35. P. Helsby, J. H. Ridd, and 1. P. B. Sandall, l. Chern. Soc., Chern. Cornrnun., 825 (1981).
36. 1. H. Ridd and 1. P. B. Sandall, l. Chern. Soc., Chern. Cornrnun., 403 (1981).
37. 1. H. Ridd and 1. P. B. Sandall, l. Chern. Soc., Chern. Cornrnun., 261 (1981).
38. M. R. Draper and J. H. Ridd, l. Chern. Soc., Perkin Trans. 2, 94 (1981).
39. D. E. Irish and O. Puzic, l. Sol. Chern. 10,377 (1981).
40. Y.-N. Lee and S. E. Schwartz, l. Phys. Chern. 85, 840 (1981).
41. G. Y. Markovits, S. E. Schwartz, and L. Newman, Inorg. Chern. 20, 445 (1981).
42. A. Aziz, M. Hoharum, and M. 1. Khalil,!. Chern. Soc., Faraday Trans. 1,77,1737 (1981).
43. S. E. Aldred and D. L. H. Williams, l. Chern. Soc., Perkin Trans. 2,1021 (1981).
44. A. B. Kyte, R. Jones-Parry, and D. Whittaker, l. Chern. Soc., Chern. Cornrnun., 74
(1982).
388
References
45. M. T. Beck, A. Kath6, and L. Dozsa, Inorg. Chirn. Acta 55, L55 (1981).
46. B. C. Challis and J. R. Outram, I. Chern. Soc., Perkin Trans. 2, 693 (1982).
47. S. S. Al-Kaabi, D. L. H. Williams, R. Bonnett, and S. L. Ooi, I. Chern. Soc., Perkin
Trans. 2, 227 (1982).
48. G. Ellison and D. L. H. Williams, I. Chern. Soc., Perkin Trans. 2, 699 (1981).
49. T. A. Meyer and D. L. H. Williams, I. Chern. Soc., Perkin Trans. 2, 361 (1981).
50. J. W. Lown and S. M. S. Chauhan, I. Chern. Soc., Chern. Cornrnun., 675 (1981).
51. E. Kalatzis and P. Papadopoulos, I. Chern. Soc., Perkin Trans. 2, 239 (1981).
52. E. Kalatzis and P. Papadopoulos, I. Chern. Soc., Perkin Trans. 2, 248 (1981).
53. J. R. Penton and H. Zollinger, Helv. Chirn. Acta 64, 1717, 1728 (1981); R. P. Kelly,
J. R. Penton, and H. Zollinger, Helv. Chirn. Acta 65, 122 (1982).
54. J. E. Packer, J. Monig, and B. C. Dobson, Aust. I. Chern. 34, 1433 (1981).
55. T. Kuokkanen, Finn. Chern. Lett., 52, 81 (1981); W. Schwarz and H. Zollinger, Helv.
Chirn. Acta 64,513 (1981); J. Besse and H. Zollinger, Helv. Chirn. Acta 64,529 (1981).
56. K. G. Phelan and G. Stedman, I. Chern. Soc. Chern. Cornrnun., 299 (1981).
57. H. Huber, Ang. Chern. Int. Ed. 21, 64 (1982).
58. J. P. Calfa, K. G. Phelan, and F. T. Bonner, Inorg. Chern. 21, 521 (1982).
59. M. S. Garley and G. Stedman, I. Inorg. Nucl. Chern. 43, 2863 (1981).
60. S. B. Oblath, S. S. Markowitz, T. Novakov, and S. G. Chang, I. Phys. Chern. 85, 1017
(1981).
61. K. G. Phelan and G. Stedman, I. Chern. Res. (S), 224 (1981).
62. R. L. Van Etten and J. M. Risley, I. Arn. Chern. Soc. 103, 5633 (1981).
63. L. S. A. Dikshitulu, G. Chandrasekharam, V. H. Rao, and P. Vani, I. Inorg. Nucl.
Chern. 43, 2455 (1981).
64. J. R. Epstein, K. Kustin, and R. H. Simogi, I. Arn. Chern. Soc. 104, 712 (1982).
65. F. T. Bonner and K. A. Pearsall, Inorg. Chern. 21, 1973 (1982).
66. H. Ghazi-Bajat, R. Van Eldik, and H. Keirn, Inorg. Chirn. Acta 60,81 (1982).
67. W. G. Jackson, G. A. Lawrence, P. A. Lay, and A. M. Sargeson, I. Chern. Soc., Chern.
Cornrnun., 70 (1982).
68. V. V. Aleshin, G. N. Shirokova, and V. Va. Rosolovskii, Russ. I. Inorg. Chern. 28,
1106 (1981).
69. F. T. Bonner, H. Degani, and M. J. Akhtar, I. Arn. Chern. Soc. 103, 3739 (1981).
70. F. T. Bonner and M. J. Akhtar, Inorg. Chern. 20,3155 (1981).
71. K. A. Pearsall and F. T. Bonner, Inorg. Chern. 21, 1978 (1982).
72. D. Littlejohn and S. G. Chang, I. Phys. Chern. 86, 537 (1982).
73. S. Naito and K. Tarnaru, I. Chern. Soc., Faraday Trans. 1,78,735 (1982).
74. D. E. Hendriksen and R. E. Powell, Inorg. Chern. 21, 1693 (1982).
75. M. J. Akhtar, J. A. Balschi, and F. T. Bonner, Inorg. Chern. 21, 2216 (1982).
76. R. A. Henderson, I. Organornet. Chern. 208, C51 (1981); I. Chern. Soc. Dalton, 917
(1982).
77. H. M. Colquhoun, I. Chern. Res. (S), 274, 276 (1981).
78. C. Casewit, J. Wenninger, and J. D. Roberts, I. Arn. Chern. Soc. 103, 6248 (1981).
79. C. A. Bunton, J. R. Moffatt, and E. Rodenas, I. Arn. Chern. Soc. 104, 2653 (1982).
80. J. R. Harbour and S. L. Issler, I. Arn. Chern. Soc. 104, 903 (1982).
80a. M. N. Hughes, M. Okolow-Zubkowska, and H. L. Wallis, I. Chern. Soc., Dalton, 2009
(1981).
80b. G. Rabai and M. T. Beck, I. Chern. Soc., Dalton, 573 (1982).
81. A. A. Astanina, A. F. Garnidov, and A. P. Rudenko, Russ. I. Inorg. Chern. 26, 952
(1981).
82. R. J. Gowland and G. Stedman, I. Inorg. Nucl. Chern. 43, 2859 (1981).
83. M. R. Bennett, G. M. Brown, L. Maya, and F. A. Posey, Inorg. Chern. 21, 2461 (1982).
84. M. N. Hughes and G. Stedman, l. Chern. Soc., 284 (1963); T. D. B. Morgan, G.
Stedman, and M. N. Hughes, l. Chern. Soc. (B), 344 (1968).
85. G. Stedman, private communication.
86. S. F. Nelsen, Acc. Chern. Res. 14, 131 (1981).
87. M. A. Mathur and H. H. Sisler, Inorg. Chern. 20,426 (1981).
88. S. S. Gupta and Y. K. Gupta, Inorg. Chern. 20, 1748 (1981).
89. V. S. Srinivasan and E. S. Gould, Inorg. Chern. 20, 3176 (1981).
90. M. Mashima, F. Ikeda, T. Doi, and S. Nishikawa, Bull. Chern. Soc. lpn. 54, 3659 (1981).
91. G. P. Panigrahi and A. K. Panda, Bull. Chern. Soc. lpn. 54,1554 (1981).
92. S. N. Mahapatro, A. K. Panda, and G. P. Panigrahi, Bull. Chern. Soc. lpn. 54, 2507
(1981).
93. F. H. Westheimer, Chern. Rev. 81, 313 (1981).
94. A. C. Satterthwait and F. H. Westheimer, l. Am. Chern. Soc. 103, 1177 (1981).
95. F. Ramirez, J. F. Marecek, and S. S. Yemul, l. Am. Chern. Soc. 104, 1345 (1982).
96. T. Eiki and W. Tagaki, Bull. Chern. Soc. lpn. 55,1102 (1982).
97. J. Rahil and P. Haake, l. Am. Chern. Soc. 103, 1723 (1981).
98. R. A. Holwerda and M. L. Ettel, Inorg. Chern. 21, 830 (1982).
99. S. S. Krishnamurthy and P. M. Sundaram, l. Chern. Soc., Dalton, 67 (1982).
100. J. M. E. Goldschmidt and E. Licht, l. Chern. Soc., Dalton, 107 (1981).
101. B. A. Moyer, B. K. Sipe, and T. J. Meyer, Inorg. Chern. 20, 1475 (1981).
102. E. Lindner and J. C. Wuhrmann, Chern. Ber. 114, 2272 (1981).
103. A. K. Bhattacharya and G. Thyagarajan, Chern. Rev. 81, 415 (1981).
104. J. Chojnowski, M. Cypryk, and J. Michalksi, l. Organornet. Chern. 215, 355 (1981).
105. K. Schafer and K.-D. Asmus, l. Phys. Chern. 85,852 (1981).
106. A. K. Indrayan, S. K. Mishra, and Y. K. Gupta, Inorg. Chern. 20, 450 (1981).
107. A. K. Indrayan, S. K. Mishra, and Y. K. Gupta,Inorg. Chern. 20,1924 (1981).
108. c. D. Baer, J. O. Edwards, and P. H. Rieger, Inorg. Chern. 20, 905 (1981).
109. P. R. Ogilby and C. S. Foote, l. Am. Chern. Soc. 103, 1219 (1981).
110. L. E. Manring and C. S. Foote, l. Phys. Chern. 86, 1257 (1982).
111. M. Hoshino, M. Nakajuma, M. Takakubo, and M. Imamura, l. Phys. Chern. 86, 221
(1982).
112. B. H. J. Bielski and J. M. Gebicki, l. Am. Chern. Soc. 104,796 (1982).
113. E. J. Nanni, R. R. Birge, L. M. Hubbard, M. M. Morrison, and D. T. Sawyer, Inorg.
Chern. 20, 737 (1981).
114. K. Umemoto, T. Sacki, N. Matsuura, and K. Motegi, Bull. Chern. Soc. lpn. 55, 746
(1982).
115. D.-H. Chin, G. Chiericato, E. J. Nanni, and D. T. Sawyer, l. Am. Chern. Soc. 104,
1296 (1982).
116. E. J. Nanni, C. T. Angelis, J. Dickson, and D. T. Sawyer, l. Am. Chern. Soc. 103,4268
(1981).
117. E. J. Nanni, D. T. Sawyer, S. S. Ball, and T. C. Bruice, l. Am. Chern. Soc. 103, 2797
(1981).
118. K. Sehested, J. Holeman, E. Bjergbakke, and E. J. Hart,!. Phys. Chern. 86, 2064 (1982).
119. J. Holeman, K. Sehested, E. Bjergbakke, and E. J. Hart, l. Phys. Chern. 86, 2069 (1982).
120. L. Forni, D. Bahneman, and E. J. Hart, l. Phys. Chern. 86, 255 (1982).
121. K. Haruta and T. Takeyama, l. Phys. Chern. 85, 2383 (1981).
122. L. J. Csanyi, Z. M. Galbacs and L. Nagy, l. Chern. Soc., Dalton, 237 (1982); L. Nagy,
Z. M. Galbacs, L. J. Csanyi, and L. Horvath, l. Chern. Soc., Dalton, 859 (1982).
123. Z. M. Galbacs, L. Nagy, and L. J. Csanyi, Polyhedron 1, 175 (1982).
390 References
124. N. Oishi, Y. Nishida, and S. Kida, Chern. Lett., 409 (1982).
125. P. Banerjee and M. P. Pujari, Bull. Chern. Soc. Ipn. 54, 2496 (1981).
126. M. P. Heyward and C. F. Wells, 1. Chern. Soc., Dalton, 1863 (1981).
127. E. N. Rizkalla, O. H. EI-Shafey, and N. M. Guindy, Inorg. Chirn. Acta 57, 199 (1982).
128. M. Otto, J. Lerchner, T. Pap, H. Zwanziger, E. Hoyer, J. Inczedy, and G. Werner, 1.
Inorg. Nucl. Chern. 43, 1101 (1981).
129. Y. Ogata and K. Tanake, Can. 1. Chern. 59, 718 (1981).
130. N. Ganapathisubramanian and R. M. Noyes, 1. Phys. Chern. 85, 1103 (1981).
131. J. M. Albrich, C. A. McCarthy, and J. K. Hurst, Proc. Natl. Acad. Sci. U.S.A. 78, 210
(1981).
132. J. K. Hurst, P. A. G. Carr, F. E. Hovis, and R. J. Richardson, Inorg. Chern. 20, 2435
(1981).
133. E. Bjergbakke, S. Navaratnam, B. J. Parsons, and A. J. Swallow, 1. Arn. Chern. Soc.
103,5926 (1981).
134. H. A. Liebhafsky, R. Furuichi, and G. M. Roe, 1. Arn. Chern. Soc. 103, 51 (1981).
135. M. N. Schuchman and C. von Sonntag, 1. Phys. Chern. 86, 1994 (1982).
136. K.-O. Hiller, B. Masloch, M. Gobi, and K.-D. Asmus, 1. Arn. Chern. Soc. 103, 2734
(1981).
137. P. Morliere and L. K. Patterson, Inorg. Chern. 21, 1833 (1982).
138. D. Bahnemann and E. J. Hart, 1. Phys. Chern. 86, 252 (1982).
139. H. Boucher, A. M. Sargeson, D. F. Sangster, and J. C. Sullivan, Inorg. Chern. 20, 3719
(1981).
140. S. S. Gupta and Y. K. Gupta, Inorg. Chern. 20,454 (1981).
141. P. Banerjee and M. P. Pujari, Z. Anorg. Allg. Chern. 473, 224 (1981).
142. D. Meyerstein, 1. Inorg. Nucl. Chern. 43, 401 (1981).
146. T. Pandurengan and P. Maruthamuthu, Bull. Chern. Soc. Ipn. 54, 3551 (1981).
147. R. K. Panda, G. Neogi, and D. Ramaswamy, Bull. Chern. Soc. Ipn. 55, 587 (1982).
148. R. E. Connick, T. M. Tam, and E. von Deuster, Inorg. Chern. 21, 103 (1982).
149. J. M. Anast and D. W. Margerum, Inorg. Chern. 20, 2319 (1981).
150. A. A. EI-Awady and G. M. Harris, Inorg. Chern. 20, 1660,4251 (1981); A. C. Dash,
A. A. EI-Awady, and G. M. Harris, Inorg. Chern. 20, 3160 (1981).
151. P. Collings, M. Garley, and G. Stedman, 1. Chern. Soc., Dalton, 331 (1981).
152. L. S. A. Dikshitulu, P. Vani, and V. H. Rao, 1. Inorg. Nucl. Chern. 43,1261 (1981).
153. L. S. A. Dikshitulu, P. Vani, and V. H. Rao, Inorg. Nucl. Chern. Lett. 17, 187 (1981).
154. P. Granger, S. Chapelle, W. R. McWhinnie, and A. AI-Rubaie, 1. Organornet. Chern.
220, 149 (1981).
155. D. P. Ip, C. D. Arthur, R. E. Winans, and E. H. Appelman, 1. Arn. Chern. Soc. 103,
1964 (1981).
156. W. V. Steele, P. A. G. O'Hare, and E. H. Appelman, Inorg. Chern. 20,1022 (1981).
157. R. C. Thompson and E. H. Appelman, Inorg. Chern. 20, 2114 (1981).
158. T. E. Eriksen, J. Lind, and G. Merenyi,J. Chern. Soc., Faraday Trans. 1,77,2115 (1981).
159. G. Schmitz and H. Rooze, Can. 1. Chern. 59,1177 (1981).
160. J. L. Grant, P. De Kepper, 1. R. Epstein, K. Kustin, and M. Orban, Inorg. Chern. 21,
2192 (1982).
161. A. H. Khan and W. C. E. Higginson, I. Chern. Soc., Dalton, 2537 (1981).
162. H. C. Kelly, K. J. Parigi, 1. Wilson, D. M. Davies, P. Jones, and L. J. Roettger, Inorg.
Chern. 20, 1086 (1981).
lti3. I. Wilson and H. C. Kelly, [norg. Chem. 21, 1622 (1982).
164. Y. Ogata, M. Kimura, and Y. Kondo, Bull. Chem. Soc. Jpn. 54, 2057 (1981).
165. J. P. Guthrie, J. Cossar, and A. Klym, J. Am. Chem. Soc. 104, 895 (1982).
166. Yu. N. Kozlov, T.P. Vorob'eva, and A. P. Purmal, Russ. 1. Phys. Chem. 55, 1294
(1981).
167. M. Soulard, F. Bloc, and A. Hatterer, J. Chem. Soc., Dalton, 2300 (1981).
168. R. J. Field, N. V. Raghavan, and J. G. Brummer, J. Phys. Chem. 86, 2443 (1982).
169. P. Guardado, A. Maestre, and M. Balon, J. [norg. Nucl. Chem. 43, 1391 (1981).
170. A. Y. Kassim and Y. Suifab, [norg. Chem. 20, 506 (1981).
171. U. K. Kliining, K. Sehested, and T. Wolff, J. Chem. Soc., Faraday Trans. 1 77,1707
(1981).
172. L. I. Elding and L. F. Olsson, [norg. Chem. 21, 779 (1982).
173. J. M. T. Rayeheba and D. W. Margerum, [norg. Chem. 20, 1441 (1981).
174. J. M. T. Rayeheba and D. W. Margerum, [norg. Chem. 20, 45 (1981).
175. G. Nord, B. Pedersen, E. Floryan-Lovborg, and P. Pagsberg, [norg. Chem. 21, 2327
(1982).
176. P. R. Young and L.-S. Hsieh, J. Am. Chem. Soc. 104, 1612 (1982).
177. D. Edelson and V. M. Thomas, 1. Phys. Chem. 85,1555 (1981).
178. P. C. Fife, J. Phys. Chem. 85, 2861 (1981).
179. D. Edelson, J. Phys. Chem. 85, 2861 (1981).
180. S. Sakanoue and M. Endo, Bull. Chem. Soc. Jpn. 55, 1406 (1982).
181. J. L. Hudson and J. C. Mankin, J. Chem. Phys. 74, 6171 (1981).
182. J. Rinzel and W. C. Troy, J. Chem. Phys. 76,1775 (1982).
183. P. De Kepper and J. Boissonade, J. Chem. Phys. 75, 189 (1981).
184. K. Iwamoto and M. Seno, Bull. Chem. Soc. Jpn. 54, 668 (1981).
185. N. Ganapathisubramanian and R. M. Noyes, 1. Chem. Phys. 76, 1770 (1982).
186. P. Sevcik and L. Adamcikova, Coli. Czech. Chem. Commun. 47, 891 (1982).
187. P. K. R. Nair, A. Mittal, and K. Srinivasulu, Bull. Chem. Soc. Jpn. 54, 317 (1981).
188. K. Showalter, J. Phys. Chem. 85, 440 (1981).
189. W. Geiseler and K. Bar-Eli, 1. Phys. Chem. 85, 908 (1981).
190. M. Orban, P. De Kepper, and I. R. Epstein, J. Am. Chem. Soc. 104, 2657 (1982).
191. K. Bar-Eli, in Non-linear Phenomena in Chemical Dynamics, C. Vidal and A. PacQult,
eds. (Springer Verlag, Berlin, 1981), p. 228.
192. S. D. Furrow and R. M. Noyes, J. Am. Chem. Soc. 104, 38 (1982).
193. S. D. Furrow and R. M. Noyes, 1. Am. Chem. Soc. 104,42 (1982).
194. R. M. Noyes and S. D. Furrow, J. Am. Chem. Soc. 104,45 (1982).
195. S. D. Furrow, J. Phys. Chem. 85, 2026 (1981).
196. P. De Kepper, I. R. Epstein, and K. Kustin, J. Am. Chem. Soc. 103,2133 (1981).
197. G. A. Papsin, A. Hanna, and K. Showalter, J. Phys. Chem. 85, 2575 (1981).
198. P. De Kepper, I. R. Epstein, and K. Kustin, 1. Am. Chem. Soc. 103, 6121 (1981).
199. T. A. Gribsehaw, K. Showalter, D. L. Banville, and I. R. Epstein, 1. Phys. Chem. 85,
2152 (1981).
200. C. E. Dateo, M. Orban, P. De Kepper, and I. R. Epstein, J. Am. Chem. Soc. 104, 504
(1982).
201. M. Orban, P. De Kepper, and I. R. Epstein, J. Phys. Chem. 86, 431 (1982).
202. M. Orban and I. R. Epstein, 1. Am. Chem. Soc. 103, 3723 (1981).
203. J. S. Reekley and K. Showalter, J. Am. Chem. Soc. 103, 7012 (1981).
204. A. A. Goneharov, Yu. N. Kozlov, and A. P. Purmal, Russ. J. Phys. Chem. 55, 927 (1981).
205. U.K. Klaning, K. Sehested, T. Wolff, and E. H. Appelman, J. Chem. Soc., Faraday
Trans. 1,78, 1539 (1982).
392
References
1. A. I. Stetsenko, M. A. Fresnov, and A. L. Konovalova, Russ. Chern. Rev. 50, 353 (1981).
2. J. A. Davies and F. R. Hartley, Chern. Rev. 81, 79 (1981).
3. S. G. Murray and F. R. Hartley, Chern. Rev. 81, 365 (1981).
4. M. Chanon and M. L. Tobe, Angew. Chern. Int. Ed. 21, 1 (1982).
5. R. van Eldik, D. A. Palmer, R. Schmidt, and H. Keirn, Inorg. Chirn. Acta 50, 131 (1981).
6. A. Giacomelli, F. Malatesta, and M. C. Spinetti, Inorg. Chirn. Acta 51,55 (1981).
7. R. W. Hay and P. Banerjee, J. Chern. Soc., Dalton Trans., 362 (1981).
8. M. J. Blandamer, J. Burgess, P. P. Duce, A. J. Duffield, and S. J. Hamshere, Transition
Met. Chern. 6, 368 (1981).
9. S. Bait, J. Meuldijk, and A. A. Wismeijer, Transition Met. Chern. 6, 267 (1981).
10. 1. H. Nelson, J. J. MacDonald, N. W. Alcock, and F. Mathey, Inorg. Chern. 21, 1200
(1982).
11. C. T. Hunt and A. L. Balch, Inorg. Chern. 21,1242 (1982).
12. c. T. Hunt and A. L. Balch, Inorg. Chern. 21, 1641 (1982).
13. O. Groning, T. Drakenberg, and L. I. Elding, Inorg. Chern. 21, 1820 (1982).
14. S. Bait and J. Meuldijk, Inorg. Chirn. Acta 47,217 (1981).
15. R. Romeo and M. Cusumano, Inorg. Chirn. Acta 49, 167 (1981).
16. S. J. S. Kerrison and P. J. Sadler, J. Chern. Soc., Chern. Cornrnun., 61 (1981).
17. c. P. Hicks and M. Spiro, J. Chern. Soc., Chern. Cornrnun., 131 (1981).
18. G. W. Bushnell, K. R. Dixon, D. T. Eady, and S. R. Stobart, Inorg. Chern. 20, 1545
(1981).
19. A. F. M. J. van der Ploeg, G. van Koten, and K. Vrieze, J. Organornet. Chern. 222, 155
(1981).
20. J. Kuyper, Inorg. Chern. 17, 1458 (1978).
21. A. F. M. 1. van der Ploeg, G. van Koten, and K. Vrieze, J. Organornet. Chern. 226, 93
(1982).
22. A. F. M. J. van der Ploeg, G. van Koten, and A. L. Spek, Inorg. Chern. 21, 2014 (1982).
23. A. F. M. J. van der Ploeg, G. van Koten, J. E. J. Schmitz, and J. G. M. van der Linden,
Inorg. Chirn. Acta 58,53 (1982).
24. A. F. M. J. van der Ploeg, G. van Koten, and K. Vrieze, Inorg. Chirn. Acta 58,35 (1982).
25. J. K. Jawad, R. J. Puddephatt, and M. A. Stalteri, Inorg. Chern. 21, 332 (1982).
26. N. J. Kermode, M. F. Lappert, B. W. Skelton, A. H. White, and J. Holton, J. Organornet.
Chern. 228, C71 (1982).
27. R. Feser and H. Werner, Angew. Chern. Int. Ed. 19,940 (1980).
28. J. S. Coe and E. Mentasti, J. Chern. Soc., Dalton Trans., 137 (1981).
30. (a) J. S. Coe and P. L. Rispoli, J. Chern. Soc., Dalton Trans., 2215 (1976); (b) E. Mentasti
and E. Pelizzetti, J. Chern. Soc., Dalton Trans., 2605 (1973).
31. M. Cusumano, G. Guglielmo, and V. Ricevuto,/. Chern. Soc., Dalton Trans., 1722 (1981).
32. M.-C. Lim, Inorg. Chern. 20, 1377 (1981).
33. S. Matsumoto, and S. Kawaguchi, Bull. Chern. Soc. Japan 54, 1704 (1981).
34. S. Okeya, H. Sazaki, M. Ogita, T. Takemoto, Y. Onuki, Y. Nakamura, B. K. Mohapatra,
and S. Kawaguchi, Bull. Chern. Soc. Japan 54, 1978 (1981).
35. S. Okeya, Y. Nakamura, and S. Kawaguchi, Bull. Chern. Soc. Japan 54,3396 (1981).
36. L. Cattalini, G. Marangoni, G. Michelon, G. Paolucci, and M. L. Tobe, Inorg. Chern.
20,71 (1981).
37. M. Bonivento, L. Canovese, L. Cattalini, G. Marangoni, G. Michelon, and M. L. Tobe,
Inorg. Chern. 20, 1493 (1981).
38. M. Bonivento, L. Canovese, L. Cattalini, G. Marangoni, G. Michelon, and M. L. Tobe,
Inorg. Chern. 20, 3728 (1981).
39. L. Canovese, L. Cattalini, G. Marangoni, G. Michelon, and M. L. Tobe, Inorg. Chern.
20,4166 (1981).
40. A P. Schwab, M. L. Tobe, and R. Romeo, Inorg. Chirn. Acta 58, 161 (1982).
41. M. L. Tobe, A P. Schwab, and R. Romeo, Inorg. Chern. 21, 1185 (1982).
42. G. Annibale, L. Maresca, L. Cattalini, and G. NatiIe, J. Chern. Soc., Dalton Trans., 1
(1982).
43. M. K. Cooper and 1. M. Downes, J. Chern. Soc., Chern. Cornrnun., 381 (1981).
44. S. Okeya, T. Miyamoto, S. Ooi, Y. Nakamura, and S. Kawaguchi, Inorg. Chirn. Acta 45,
Ll35 (1980).
45. J. H. Nelson and N. W. Alcock, Inorg. Chern. 21,1196 (1982).
46. R. Favez and R. Roulet, Inorg. Chern. 20, 1598 (1981).
47. (a) H. van der Poel, G. van Koten, M. Kokkes, and C. H. Starn, Inorg. Chern. 20, 2941
(1981); (b) H. van der Poe I and G. van Koten, Inorg. Chern. 20, 2950 (1981).
48. H. van der Poel, G. van Koten, D. M. Grove, P. S. Pregosin, and K. A O. Starzewski,
Helv. Chirn. Acta 64, 1174 (1981).
49. H. van der Poel, G. van Koten, and G. C. van Stein, J. Chern. Soc., Dalton Trans., 2164
(1981).
50. H. van der Poel, G. van Koten, and K. Vrieze, Inorg. Chirn. Acta 51,241 (1981).
51. N. K. Roberts and S. B. Wild, Inorg. Chern. 20,1892,1900 (1981).
52. G. Annibale, L. Canovese, L. Cattalini, G. Natile, M. Biagini-Cingi, A-M. Manotti-
Lanfredi, and A Tiripicchio, J. Chern. Soc., Dalton Trans., 2280 (1981).
53. D. J. A de Waal, T. I. A Gerber, and W. J. Louw, J. Chern. Soc., Chern. Cornrnun.,
100 (1982).
54. D. J. A de Waal, T. I. A. Gerber, W. J. Louw, and R. van Eldik, Inorg. Chern. 21, 2002
(1982).
55. (a) H. Tanaka, K. Isobe, and S. Kawaguchi, Chern. Lett., 769 (1981); (b) H. Tanaka, K.
Isobe, and S. Kawaguchi, Inorg. Chirn. Acta 54, L201 (1981).
56. J. P. Fackler and L. D. Thompson, Inorg. Chirn. Acta 48,45 (1981).
57. W. J. Louw and R. van Eldik, Inorg. Chern. 20, 1939 (1981).
58. O. J. Scherer and H. Jungmann, J. Organornet. Chern. 228, C61 (1982).
59. (a) T. J. McCarthy, R. G. Nuzzo, and G. M. Whitesides, J. Arn. Chern. Soc. 103, 1676,
(1981); (b) J. A. Ibers, R. DiCosimo, and G. M. Whitesides, Organornetallics 1, 13 (1982).
60. K. Tatsumi, R. Hoffmann, A. Yamamoto, and J. K. Stille, Bull. Chern. Soc. Japan 54,
1857 (1981).
61. F. Ozawa, T. Ito, Y. Nakamura, and A Yamamoto, Bull. Chern. Soc. Japan 54, 1869
(1981).
62. C. W. Rice and R. S. Tobias, J. Organornetal. Chern. 86, C37 (1975).
63. A Gillie and J. K. Stille, I. Arn. Chern. Soc. 102, 4933 (1980).
64. M. Cusumano, G. Guglielmo, V. Ricevuto, S. Sostero, O. Traverso, and T. J. Kemp, I.
Chern. Soc., Dalton Trans., 302 (1981).
65. N. W. Alcock, T. J. Kemp, and F. L. Wimmer, J. Chern. Soc., Dalton Trans., 635 (1981).
66. R. D. Lai and A Shaver, Inorg. Chern. 20, 477 (1981).
67. L. I. Elding, A.-B. Groning, and O. Groning, J. Chern. Soc., Dalton Trans., 1093 (1981).
68. L. I. Elding and L. F. Olsson, Inorg. Chern. 21, 779 (1982).
69. G. Patel, R. S. Satchell, and D. P. N. Satchell, Inorg. Chirn. Acta 54, L97 (1981).
70. R. J. Cross and I. G. Phillips, J. Chern. Soc., Dalton Trans., 2132 (1981).
71. A B. Goel, S. Goel, D. van Derveer, and C. G. Brinkley, Inorg. Chirn. Acta 64, Ll73
(1982).
394 References
72. G. K. Anderson, H. C. Clark, and J. A. Davies, Inorg. Chern. 20, 944 (1981).
73. P. Zanello, R. Seeber, and A. Cinquantini, J. Inorg. Nucl. Chern. 43,1095 (1981).
74. C. E. Briant, K. A. Rowland, C. T. Webber, and D. M. P. Mingos, J. Chern. Soc., Dalton
Trans., 1515 (1981).
75. S. AI-Jibori, C. Crocker, and B. L. Shaw, J. Chern. Soc., Dalton Trans., 319 (1981).
76. C. T. Hunt and A. L. Balch, Inorg. Chern. 20, 2267 (1981).
77. R. H. Hill and R. J. Puddephatt, Inorg. Chirn. Acta 54, L277 (1981).
78. D. J. A. de Waal, T. I. A. Gerber, and W. J. Louw, Inorg. Chern. 21, 1259 (1982).
79. J. H. Coates, D. A. Hadi, S. F. Lincoln, H. W. Dodgen, and J. P. Hunt, Inorg. Chern.
20,707 (1981).
80. M. Kodama and E. Kimura, J. Chern. Soc., Dalton Trans., 694 (1981).
1. P. Moore, this series, Vol. 1.
2. L. F. Larkworthy, Coord. Chern. Rev. 37, 91 (1981).
3. S. Asperger, Chern. Abs. 95, 107598g (1981).
5. H. Cohen and D. Meyerstein, J. Chern. Soc., Dalton Trans., 2559 (1974).
6. A. Bakac and J. H. Espenson, J. Arn. Chern. Soc. 103, 2721, 2728 (1981).
7. D. A. Ryan and J. H. Espenson, J. Arn. Chern. Soc. 104, 704 (1982).
8. G. W. Kirkes, A. Bakac, and J. H. Espenson, J. Arn. Chern. Soc. 104, 1249 (1982).
9. A. Bakac, J. H. Espenson, and L. P. Miller, Inorg. Chern. 21, 1557 (1982).
10. P. J. Hansen and J. P. Birk, Int. J. Chern. Kinet. 13, 1203 (1981).
11. 1. Labuda, D. I. Bustin, and J. Mocak, Chern. Abs. 95, 176437y (1981).
12. L. Mf(lnsted and O. Mf(lnsted, Acta Chern. Scand. 36, 365, 555 (1982).
13. P. Riccieri and E. Zinato, J. Inorg. Nucl. Chern. 43, 739 (1981).
14. A. Creix and M. Ferrer, Inorg. Chirn. Acta 59, 177 (1982).
15. P. Riccieri and E. Zinato, Inorg. Chern. 20, 3722 (1981).
16. M. Delaver and P. J. Staples, J. Chern. Soc., Dalton, 981 (1981).
17. J. C. Chang, Inorg. Chern. 21, 837 (1982).
18. J. C. Chang and J. W. Vaughn, Inorg. Chern. 21, 2512 (1982).
19. R. G. Swisher, G. A. Brown, R. C. Smierciak, and E. L. Blinn, Inorg. Chern. 20, 3947
(1981).
20. D. Yang and D. A. House, Inorg. Chirn. Acta Lett. 64, L167 (1982).
21. H. Ogino, M. Shimura, and N. Tanaka, Inorg. Chern. 21, 126 (1982).
22. A. K. Basak, D. Banerjea, R. W. Hay, and C. Chatterjee, J. Coord. Chern. 11, 195 (1981).
23. M. Casula, G. I1Iuminat, and G. Ortaggi, Inorg. Chern. 11, 1062 (1972).
24. S. Wajda, Chern. Abs. 95, 50184v (1981).
25. M. Kostanski and S. Magas, Chern. Abs. 96, 92431 (1982).
26. M. Thompson and R. E. Connick, Inorg. Chern. 20, 2279 (1981).
27. I. A. Khan and K. U. Din, J. Inorg. Nuc!. Chern. 43, 1082 (1981).
28. M. Bhattacharya and G. S. De, Indian J. Chern. Sec. A. 20A, 780 (1981).
29. R. D. Williams, D. E. Pennington, and W. B. Smith, Inorg. Chirn. Acta 58,45 (1982).
30. Y. Sakabe and Y. Matsumato, Bull. Chern. Soc. Japan, 54,1253 (1981).
31. V. Holba and M. Talapka, Chern. Zvesti 35,447 (1981).
32. D. R. Prasad, T. Ramasami, D. Ramaswamy, and M. Santappa, Inorg. Chern. 21, 850
(1982).
395
33. J. W. Vaughan, Inorg. Chern. 20, 2397 (1981).
34. M. J. Root and E. Deutsch, Inorg. Chern. 20,4376 (1981).
35. P. O'Brien and D. A. Sweigart, Inorg. Chern. 21, 2094 (1982).
36. J. G. Leipoldt, S. S. Basson, and D. R. Rabie, J. Inorg. Nucl. Chern. 12, 3239 (1981).
37. G. Ali and N. A. Lewis, J. Chern. Soc., Chern. Cornrnun., 715 (1982).
38. W. A. Wickramasinghe, P. H. Bird, M. A. Jamieson, N. Serpone, and M. Maestri, Inorg.
Chirn. Acta 64, L85 (1982).
39. I. Smidova, A. Vlcek, and A. A. Vlcek, Inorg. Chirn. Acta Lett. 64, L63 (1982).
40. A. D. Kirk, Coord. Chern. Rev. 39, 225 (1981).
41. M. A. Jamieson, N. Serpone, and M. Z. Hoffman, Coord. Chern. Rev. 39,121 (1981).
42. K. Angermann, R. Schmidt, R. Van Eldik, H. Kelm, and F. Wasgestian, Inorg. Chern.
21, 1175 (1982).
43. P. Riccieri and E. Zinato, Inorg. Chirn. Acta 52, 133 (1981).
44. A. D. Kirk, J. Phys. Chern. 85, 3205 (1981).
45. M. C. Cimolino and R. G. Linck, Inorg. Chern. 20, 3499 (1981).
46. X. Yang, C. A. Sutton, and C. Kutal, Inorg. Chern. 21, 2893 (1982).
47. R. Fukuda, R. T. Walters, H. Macke, and A. W. Adamson,!. Phys. Chern. 83, 2097 (1979).
48. N. Serpone, M. A. Jamieson, R. Sriram, and M. Z. Hoffman,Inorg. Chern. 20, 3983 (1981).
49. V. Balzani and F. Bolletta, J. Photochern. 17,479 (1981).
50. B. OIarte, H. Krentzien, and C. Bifano, Chern. Abs. 95, 159743c (1981).
51. K. Miyoshi, Y. Matsumoto, and H. Yoneda, Inorg. Chern. 21, 790 (1982).
52. S. I. Arshankov and A. L. Poznyak, Z. Anorg. AUg. Chern. 481, 201 (1981).
53. S. I. Arshankov and A. L. Poznyak, Russ. J. Inorg. Chern. 26, 850 (1981).
54. K. Uchida and Y. Takinami, Bull. Chern. Soc. Japan 54,2298 (1981).
55. D. Huchital and X. C. Yang, J. Coord. Chern. 11, 57 (1981).
56. D. A. House, Aust. J. Chern. 35, 659 (1982).
57. D. A. House, Inorg. Chirn. Acta 54, L145 (1981).
58. R. Tsuchiya, A. Uehara, and T. Yoshikuni, Inorg. Chern. 21, 590 (1982).
59. R. Tsuchiya and A. Euhara, Therrnochirn. Acta 50,93 (1981).
60. J. Ribas and J. Casabo, Therrnochirn. Acta 47, 271 (1981).
61. K. Akabori, J. Inorg. Nucl. Chern. 43, 677 (1981).
62. K. Nakano, Y. Narusawa, and H. Moroi, Bull. Chern. Soc. Japan 54, 2529 (1981).
1. R. W. Hay, Coord. Chern. Rev. 41, 191 (1982).
2. D. A. Palmer and H. Kelm, Coord. Chern. Rev. 36, 89 (1981).
3. G. A. Lawrence, Inorg. Chirn. Acta 54, L225 (1981).
4. M. J. Sisley and T. W. Swaddle, Inorg. Chern. 20, 2799 (1981).
5. G. Daffner, D. A. Palmer, and H. Kelm, Inorg. Chirn. Acta 61, 57 (1982).
6. J. L. Laird and R. B. Jordan, Inorg. Chern. 21, 855 (1982).
7. D. A. Buckingham, P. J. Cresswell, A. M. Sargeson, and W. G. Jackson, Inorg. Chern.
20, 1647 (1981).
8. J. O. Edwards, F. Monacelli, and G. Ortaggi, Inorg. Chirn. Acta 11,47 (1974).
9. W. C. Kupferschmidt and R. B. Jordan, Inorg. Chern. 21, 2089 (1982).
10. R. W. Hay, P. R. Norman, D. A. House, and C-K. Poon,Inorg. Chirn. Acta 48, 81 (1981).
11. W. G. Jackson, Inorg. Chirn. Acta. 47, 159 (1981).
12. W. Rindermann and R. Van Eldik, Inorg. Chirn. Acta. 64, L203 (1982).
396
References
13. A. C. Dash, M. S. Dash, and S. K. Mohapatra, J. Inorg. Nucl. Chem. 43,1293 (1981).
14. B. S. Rao, R. Nanda, and K. K. Tripathy, Transition Met. Chem. 6,97 (1981).
15. V. Holba and O. Grancicova, J. Inorg. Nucl. Chem. 43, 2071 (1981).
16. W. G. Jackson and C. M. Begbie, Inorg. Chim. Acta. 60,115 (1982).
17. M. M. Muir and J. A. Diaz, Syn. React. Inorg. Met.-Org. Chem.11, 333 (1981); Chem.
Abstr. 95, 68668.
18. S.-O. Oh, G. Roessling, and H. Lentz, Z. Phys. Chem. (Weisbaden) 125, 183 (1981);
Chem. Abstr. 95,139419.
19. M. Sugimura, T. Okubo, and N. Ise, Macromolecules 14, 124 (1981); Chem. Abstr. 94,
84787.
20. G. P. Syrtsova, K. S. Kynoheva, and M. M. Demieva, Koord. Khim. 7, 103 (1981);
Chem. Abstr. 94, 128104.
21. D. A. Buckingham, C. R. Clark, and W. S. Webley, J. Chem. Soc., Dalton, 2255 (1980).
22. D. A. House and J. W. Blunt, Inorg. Chim. Acta 49, 193 (1981).
23. D. A. House, Inorg. Chim. Acta 51,273 (1981).
24. D. A. House, A. R. Gainsford, and J. W. Blunt, Inorg. Chim. Acta 57, 141 (1982).
25. M. Iida, E. Kai, K. Nishimoto, and H. Yamatera, Bull. Chem. Soc. Japan 54, 1818
(1981).
26. M. Booij, Inorg. Chim. Acta 55, 109 (1981).
27. A. Dhur, S. Das, R. N. Banerjee, and D. Banerjea, Transition Met. Chem. 7, 125 (1982).
28. M. L. Tobe, Acc. Chem. Res. 3, 377 (1970).
29. A. M. Sargeson, Pure Appl. Chem. 33, 527 (1973).
30. W. G. Jackson and A. M. Sargeson, in Rearrangements in Ground and Excited States,
Vol. 2, P. de Mayo, ed. (Academic Press, New York, 1980), pp. 321-335.
31. N. E. Dixon, W. G. Jackson, W. Marty, and A. M. Sargeson,Inorg. Chem. 21, 688 (1982).
32. N. E. Dixon, C. Gazzola, R. L. Blakely, and B. Zerner, J. Am. Chem. Soc. 97, 4131
(1975).
33. N. E. Dixon, P. W. Riddles, C. Gazzola, R. L. Blakely, and B. Zerner, Can. J. Biochem.
58, 1335 (1980).
34. R. L. Blakely, A. Treston, R. K. Andrews, and B. Zerner, J. Am. Chem. Soc. 104, 612
(1982).
35. U. Tinner and W. Marty, Inorg. Chem. 20, 3750 (1981).
36. F. R. Nordmeyer, Inorg. Chem. 8, 2780 (1969).
37. R. A. Henderson and M. L. Tobe, Inorg. Chem. 16, 2576 (1977).
38. R. W. Hay, D. A. House, and P. R. Norman, Inorg. Chim. Acta 45, L117 (1980).
39. S. Bait, W. E. Renkema, and P. C. M. Van Zijl, Inorg. Chim. Acta. 45, L241 (1980).
40. R. W. Hay and P. R. Norman, Transition Met. Chem. 6, 4 (1981).
41. K. Ogino and H. Seki, Bull. Chem. Soc. Japan 54,719 (1981).
42. A. C. Dash and G. M. Harris, Inorg. Chem. 20,4011 (1981).
43. D. A. Buckingham, C. R. Clark, B. M. Foxman, G. J. Gainsford, A. M. Sargeson, M.
Wein, and A. Zanella, Inorg. Chem. 21, 1986 (1982).
44. K. B. Nolan and R. W. Hay, J. Chem. Soc., Dalton, 914 (1974).
45. W. G. Jackson and C. M. Begbie, Inorg. Chem. 20, 1654 (1981).
46. M. J. Saliby, D. West, and S. K. Madan, Inorg. Chem. 20, 723 (1981).
47. A. E. Eid and C. F. Wells, J. Chem. Soc., Faraday Trans., 1621 (1981).
48. H. Ghazi-Bajat, R. Van Eldik, and H. Keirn, Inorg. Chim. Acta 60,81 (1982).
49. J. M. Coronas, R. Vicente, and M. Ferrer, Inorg. Chim. Acta 49,259 (1981).
50. A. C. Dash, R. K. Nanda, and N. Ray, J. Coord. Chem. 11, 213 (1982).
51. R. van Eldik and G. M. Harris, Inorg. Chem. 19, 3684 (1980).
52. R. van Eldik, Inorg. Chim. Acta 49,5 (1981).
53. M. B. Davies, I. Inorg. Nucl. Chern. 43,1277 (1981).
54. M. B. Davies and J. W. Lethbridge, I. Inorg. Nucl. Chern. 43,1579 (1981).
55. L. S. Bark, M. B. Davies, and M. C. Powell, Inorg. Chirn. Acta. 50,195 (1981).
56. M. G. Burnett and W. M. Gilfillan, I. Chern. Soc., Dalton Trans., 1578 (1981).
57. S. Funahashi, M. Inamo, K. Ishihara, and M. Tanaka, Inorg. Chern. 21,447 (1982).
58. A. Ghoshal and S. K. Siddhanta, Indian I. Chern. 20A, 40 (1981).
59. A. Ghoshal and S. K. Siddhanta, Indian I. Chern. 20A, 661 (1981).
60. M. Glavas, M. S. EI-Nasr, and W. L. Reynolds, Inorg. Chern. 20, 751 (1981).
61. W. Gregory Jackson, Aust. I. Chern. 34, 215 (1981).
62. R. Dreos-Garlatti, G. Tauzher, G. Costa, and M. Green, Inorg. Chirn. Acta. 50, 95
(1981).
63. J. H. Ramsden, Diss. Abstr. Int. B. 41, 3442 (1981); Univ. Microfilms, Int. Order No.
8106636.
64. M. B. Celap, J. C. Bailar, Jr., and J. K. Beattie, Inorg. Chirn. Acta. 47, 59 (1980).
65. G. Schiavon and C. Paradisi, Gazz. Chirn. Itat. 111, 207 (1981).
66. G. McLendon and A. E. Martell, Coord. Chern. Rev. 19, 1 (1976).
67. A. B. P. Lever and H. B. Gray, Acc. Chern. Res. 11, 348 (1978).
68. R. D. Jones, D. A. Summerville, and F. Basolo, Chern. Rev. 79,139 (1979).
69. Y. Sasaki, K. Z. Suzuki, A. Matsumoto, and K. Saito, Inorg. Chern. 21, 1825 (1982).
70. C-L. Wong and J. F. Endicott, Inorg. Chern. 20, 2233 (1981).
71. S. Fallab, H-P. Hunold, M. Maeder, and P. R. Mitchell, I. Chern. Soc., Chern. Cornrnun.,
469 (1981).
72. A. A. EI-Awady and G. M. Harris,Inorg. Chern. 20, 1660 (1981).
73. A. C. Dash, A. A. EI-Awady, and G. M. Harris, Inorg. Chern. 20, 3160 (1981).
74. A. A. EI-Awady and G. M. Harris, Inorg. Chern. 20, 4251 (1981).
75. A. C. Dash and G. M. Harris, Inorg. Chern. 21, 1265 (1982).
76. J. G. Leipoldt, S. S. Basson, G. J. Lamprecht, and D. R. Rabie, Inorg. Chirn. Acta 51,
67 (1981).
77. K. R. Ashley and J. G. Leipoldt, Inorg. Chern. 20, 2326 (1981).
78. M. Nishizawa and P. C. Ford, Inorg. Chern. 20, 2016 (1981).
79. K. Angermann, R. Schmidt, R. van Eldik, H. KeIrn, and F. Wasgestian, Inorg. Chern.
21, 1175 (1982).
80. K. Angermann, R. van Eldik, H. Kelm, and F. Wasgestian, Inorg. Chirn. Acta 49, 247
(1981).
81. M. A. R. Scandola, Inorg. Chirn. Acta 54, L159 (1981).
82. M. Nakashima and S. Kida, Bull. Chern. Soc. Japan 55, 809 (1982).
83. J. L. Reed, Inorg. Chern. 20, 2590 (1981).
84. c. H. Langford and R. L. P. Sasseville, Can. J. Chern. 59, 647 (1981).
85. V. H. Houlding, H. Macke, and A. W. Adamson, Inorg. Chern. 20, 4279 (1981).
86. W. Bottcher and A. Haim, Inorg. Chern. 21, 531 (1982).
87. I. I. Creaser, J. MacB. Harrowfield, F. R. Keene, and A. M. Sargeson, I. Arn. Chern.
Soc. 103, 3559 (1981).
88. R. J. Balahura and W. L. Purcell, Inorg. Chern. 20, 4159 (1981).
89. D. A. Buckingham and C. R. Clark, Aust. I. Chern. 34, 1769 (1981).
90. P. R. Norman and R. D. Cornelius, I. Arn. Chern. Soc. 104,2356 (1982).
91. E. A. Merritt and M. Sundaialingam, Acta Crystallogr. B36, 2576 (1980).
92. E. A. Merritt and M. Sundaralingam, Acta Crystallogr. B37, 1505 (1981).
93. E. A. Merritt, M. Sundaralingam, and R. D. Cornelius, Acta Crystallogr. B37, 657
(1981).
94. S. F. Lincoln and D. R. Stranks, Aust. I. Chern. 21, 37, 57, 67 (1968).
398 References
95. A. R. Gainsford, R. D. Pizer, A. M. Sargeson, and P. O. Whimp, J. Am. Chem. Soc.
103,792 (1981).
96. S. Patai, ed., The Chemistry of the Azido Group (Interscience, New York, 1971).
97. R. Huisgen, Proc. Chem. Soc., 357 (1961).
98. R. Huisgen, Angew. Chem. Int. Ed. Engl. 2, 633 (1963).
99. T. Kemmerich, J. H. Nelson, N. E. Takach, H. Boehme, B. Jablonski, and W. Beck,
Inorg. Chem. 21, 1226 (1982).
100. W. R. Ellis and W. L. Purcell, Inorg. Chem. 21, 834 (1982).
101. W. P. Norris, J. Org. Chem. 27, 3248 (1962).
102. W. Fleming, J. W. Fronabarger, M. L. Leiberman, and V. M. Loyola, in Second Chemical
Conference of the North American Continent, Las Vegas, Nevada, August 1980, A.C.S:,
Washington D.C., Abstract INOR 13.
103. D. A. Buckingham and C. R. Clark, Aust. J. Chem. 35, 431 (1982).
104. R. W. Hay and R. Bembi, Inorg. Chim. Acta. 64, L179 (1982).
105. C. J. Boreham, D. A. Buckingham, D. J. Francis, A. M. Sargeson, and L. G. Warner,
J. Am. Chem. Soc. 103, 1975 (1981).
106. C. J. Boreham and D. A. Buckingham, Inorg. Chem. 20, 3112 (1981).
107. D. A. Buckingham, L. G. Marzilli, and A. M. Sargeson, J. Am. Chem. Soc. 89, 4539
(1967).
108. D. A. Buckingham, J. Dekkers, and A. M. Sargeson, J. Am. Chem. Soc. 95, 4174 (1973).
109. R. W. Hay and P. J. Morris, in Metal Ions in Biological Systems, Vol. 5, H. Sigel, ed.
(Marcel Dekker, New York, 1976), p. 173.
110. H. Wautier, V. DafJe, M.-N. Smets, and J. Fastrez, J. Chem. Soc., Dalton Trans., 2479
(1981); H. Wautier, D. Marchal, and J. Fastrez, J. Chem. Soc., Dalton Trans., 2484
(1981).
111. c. R. Clark, R. F. Tasker, D. A. Buckingham, D. R. Knighton, D. R. K. Harding, and
W. S. Hancock, J. Am. Chem. Soc. 103,7023 (1981).
112. D. R. Knighton, D. R. K. Harding, M. J. Friar, W. S. Hancock, G. D. Reynolds, C. R.
Clark, R. F. Tasker, and D. A. Buckingham, J. Am. Chem. Soc. 103,7025 (1981).
113. N. Yoshida and M. Fujimoto, Bull. Chem. Soc. Japan 53,3526 (1980).
114. K. L. Brown and R. K. Hessley, Inorg. Chim. Acta. 53, L115 (1981).
115. G. H. Schrauzer and J. H. Grate, J. Am. Chem. Soc. 103, 541 (1981).
116. J. S. Thayer, Inorg. Chem. 20, 3573 (1981).
117. N. E. Takach and J. H. Nelson, Inorg. Chem. 20, 1258 (1981).
118. T-T. Tsou, M. Loots, and J. Halpern, J. Am. Chem. Soc. 104, 623 (1982).
119. J. H. Dimmit and J. H. Weber, Inorg. Chem. 21, 700 (1982).
120. U. Sakaguchi, H. Okazaki, and H. Yoneda, Inorg. Chim. Acta 64, L175 (1982).
121. B. T. Golding, P. V. Ionannou, and P. J. Sellars, Inorg. Chim. Acta. 56, 95 (1981).
122. N. S. Rowan, C. B. Storm, and R. Rowan, J. Inorg. Biochem. 14,59 (1981).
1. A. Watanabe, H. Kido, and K. Saito, Inorg. Chem. 20,1107 (1981).
2. Y. Ikeda, S. Soya, H. Tomiyasu, and H. Fukutomi, Bull. Chem. Soc. Japan 54, 3768
(1981).
3. R. A. Henderson, G. Davies, J. R. Dilworth, and R. N. F. Thorneley, J. Chem. Soc.,
4. E. Hofer, W. Holzbach, and K. Wieghardt, Angew. Chem. Int. Ed. 20, 282 (1981).
5. B. Glavincevski and S. Brownstein, J. Inorg. Nucl. Chem. 43, 1827 (1981).
399
6. J. Burgess, J. Fawcett, R. D. Peacock, and R. Sherry, J. Fluorine Chern. 18, 173 (1981).
7. J. Fawcett, R. D. Peacock, and D. R. Russell, J. Chern. Soc., Dalton Trans., 2294 (1980).
8. Y. Ito and S. Kawaguchi, Bull. Chern. Soc. Japan 54, 150 (1981).
9. H. Spies and B. Johannsen, Inorg. Chirn. Acta 48,255 (1981).
10. C. H. Paik, F. Vieras, W. C. Eckelman, and R. C. Reba, J. Radioanal. Chern. 60, 281
(1980).
11. A. Davison, A. G. Jones, C. Orvig, and M. Sohn, Inorg. Chern. 20,1629 (1981).
12. K. J. Franklin, H. E. Howard-Lock, and C. J. L. Lock, Inorg. Chern. 21, 1941 (1982).
13. M. Eisenhut, H. J. Hermann, and K. Zum Winkel, Nuklearrnedizin. Suppl. 17, 146
(1980); NucCornpact 10, 197 (1979).
14. H. A. Friedman, ORNL-7515 (1981).
15. H. S. Trop, A. Davison, A. G. Jones, M. A. Davis, D. J. Szalda, and S. J. Lippard,
Inorg. Chern. 19, 1105 (1980).
16. V. I. Spitsyn, B. Baierl, S. V. Kryuchkov, A. F. Kuzina, and M. Varen, Doklady Chern.
256,30 (1981).
17. F. A. Cotton and L. D. Gage, Nouv. J. Chirn. 1, 441 (1977).
18. W. Preetz and G. Peters, Z. Naturf. 35b, 797 (1980).
19. K. Yoshihara, T. Omori, and H. Kido, I. Inorg. Nucl. Chern. 43, 639 (1981).
20. M. J. Buckingham, G. E. Hawkes, and J. R. Thornback, Inorg. Chirn. Acta 56, L41
(1981).
21. R. G. Kidd, I. Magn. Reson. 45, 88 (1981).
22. H. Spies and B. Johanssen, React. Kinet. Catal. Lett. 10, 153 (1979).
23. A. Davison, A. G. Jones, and M. J. Abrams, Inorg. Chern. 20,4300 (1981).
24. A. F. De Suarez, V. E. Parera, and A. E. A. Mitta, Acta Bioquirn. Clin. Latinoarner.
14,571 (1980).
25. E. Roncari, U. Mazzi, R. Rossi, A. Duatti, and L. Magon, Transition Met. Chern. 6,
169 (1981).
26. A. Duatti, R. Rossi, A. Marchi, L. Magon, E. Roncari, and U. Mazzi, Transition Met.
Chern. 6, 360 (1981).
27. E. B. Borghi, M. A. Biesa, P. J. Aymonino, and J. A. Olabe, J. Inorg. Nucl. Chern. 43,
1849 (1981).
28. D. H. Macartney and A. McAuley, J. Chern. Soc., Dalton Trans., 1780 (1981).
29. J. M. Malin, B. S. Brunschwig, G. M. Brown, and Ken-shin Kwan, Inorg. Chern. 20,
1438 (1981).
30. D. H. Macartney and A. McAuley, Inorg. Chern. 20, 748 (1981).
31. K. J. Pfenning, Liangshiu Lee, H. D. Wohlers, and J. D. Petersen, Inorg. Chern. 21,
2477 (1982).
32. W. I. K. Bisset, M. G. Burdon, A. R. Butler, C. Glidewell, and J. Reglinski, J. Chern.
Res. (S), 299, (M), 3501 (1981).
33. S. Raman, Indian J. Chern. 19A, 907 (1980).
34. S. Raman, I. Inorg. Nucl. Chern. 43,1855 (1981).
35. M. Tubino and E. J. S. Vichi, J. Chern. Soc., Dalton Trans., 1064 (1981).
36. J. R. Bertolino, I. K. Lauf, J. G. M. Lira, M. Tubino, and E. J. S. Vichi, XXII I.c.c.c.,
Budapest, Abstracts, Tu P81 (1982).
37. S. Tachiyashiki and H. Yamatera, Bull. Chern. Soc. Japan 55, 1014 (1982).
38. S. Tachiyashiki and H. Yamatera, Bull. Chern. Soc. Japan 55, 759 (1982).
39. S. Tachiyashiki and H. Yamatera, Chern. Lett., 1681 (1981).
40. H. D. Burrows, J. Ige, and S. A. Umoh, J. Chern. Soc., Faraday Trans. I 78, 947 (1982).
41. S. Tachiyashiki and H. Yamatera, Bull. Chern. Soc. Japan 54,3340 (1981).
42. L. G. Vanquickenborne and K. Pierioot, Inorg. Chern. 20, 3673 (1981).
400 References
43. G. A. Lawrance, D. R. Stranks, and T. R. Sullivan, Austral. J. Chern. 34, 1763 (1981);
and references therein.
44. E. Konig, G. Ritter, and H. A. Goodwin, Inorg. Chern. 20, 3677 (1981).
45. J. Burgess and R. H. Prince, J. Chern. Soc. (A), 434 (1967).
46. Ho-Hsiang Wei and Ching-Sung Hsiao, J. Inorg. Nucl. Chern. 43, 2299 (1981).
47. F. M. Mikhail, P. Askalani, 1. Burgess, and R. Sherry, Transition Met. Chern. 6, 51 (1981).
48. J. Burgess and C. D. Hubbard, Inorg. Chirn. Acta 64, L71 (1982).
49. R. Aruga, J. Inorg. Nucl. Chern. 43, 1859 (1981).
50. M. J. Biandamer, J. Burgess, N. V. Reed, and P. Wellings, J. Inorg. Nucl. Chern. 43,
3245 (1981).
51. M. J. Blandamer, J. Burgess, and A. J. Duffield, J. Chern. Soc., Dalton Trans., 1 (1980).
52. M. J. Biandamer, J. Burgess, J. G. Chambers, and A. J. Duffield, Transition Met. Chern.
6, 156 (1981).
53. M. J. Blandamer, J. Burgess, and P. Wellings, Transition Met. Chern. 6, 364 (1981).
54. G. Nord, B. Pedersen, E. Floryan-Lf/Jvberg, and P. Pagsberg, Inorg. Chern. 21, 2327
(1982).
55. G. van Koten and K. Vrieze, Rec. Trav. Chirn. 100, 129 (1981).
56. H. E. Toma and R. H. U. Borges, J. Coord. Chern. 11, 143 (1981).
57. N. K. Kildahl, T. J. Lewis, and G. Antonopoulos, Inorg. Chern. 20, 3952 (1981).
58. K. Umemoto, T. Saeki, N. Matsuura, and K. Mategi, Bull. Chern. Soc. Japan 55, 746
(1982).
59. I. R. Epstein, K. Kustin, and R. H. Simoyi, J. Arner. Chern. Soc. 104, 712 (1982).
60. J. Burgess, J. Chern. Soc. A, 1899 (1969).
61. C. Ercolani, F. Monacelli, G. Pennesi, G. Rossi, E. Antonini, P. Ascenzi, and M.
Brunori, J. Chern. Soc., Dalton Trans., 1120 (1981).
62. D. V. Stynes, Yat Sun Hui, and V. Chew, Inorg. Chern. 21, 1222 (1982).
63. A. Valiotti, A. Adeyemo, and P. Hambright, Inorg. Nucl. Chern. Lett. 17,213 (1981).
64. I. Collamati, Inorg. Nucl. Chern. Lett. 17, 69 (1981).
65. Y. Sasaki, Chern. Lett., 1117 (1981).
66. J. H. Cameron, A. G. Lappin, J. M. Winfield, and A. McAuley, J. Chern. Soc., Dalton
Trans., 2172 (1981).
67. R. D. Gillard, W. S. Waiters, and P. A. Williams, Transition Met. Chern. 6, 20 (1981).
68. N. V. Duffy, Inorg. Chirn. Acta 47, 31 (1981).
69. M. C. Palazzotto, D. J. Duffy, B. L. Edgard, L. Que, and L. H. Pignolet, J. Arner.
Chern. Soc. 95, 4537 (1973).
70. G. Carta, F. Cristiani, P. Deplano, A. Diaz, and E. F. Trogu, Inorg. Chirn. Acta 59,
101 (1982).
71. T. P. Tufano and K. N. Raymond, J. Arn. Chern. Soc. 103, 6617 (1981).
72. M. Grant and R. B. Jordan, Inorg. Chern. 20, 55 (1981).
73. H. W. Dodgen, G. Liu, and J. P. Hunt, Inorg. Chern. 20,1002 (1981).
74. T. W. Swaddle and A. E. Merbach, Inorg. Chern. 20,4212 (1981).
75. J. H. Espenson and R. C. McHatton, Inorg. Chern. 20, 3090 (1981).
76. D. W. Franco and H. Taube, Inorg. Chern. 17, 571 (1978).
77. D. W. Franco, Inorg. Chirn. Acta 48, 1 (1981).
78. M. M. Doeff and D. A. Sweigart, Inorg. Chern. 20, 1683 (1981).
79. C. E. Holloway, D. V. Stynes, and C. P. J. Vuik, J. Chern. Soc., Dalton Trans., 95 (1982).
80. C. M. Carr, D. M. Davies, M. Gower, L. A. P. Kane-Maguire, and D. A. Sweigart, J.
81. T. V. Ashworth, D. J. A. de Waal, and E. Singleton, J. Chern. Soc., Chern. Cornrnun.,
78 (1981).
401
82. C. Bremard, G. Nowogrocki, and S. Sueur, I. [norg. Nucl. Chern. 43, 715 (1981).
83. M. S. Thompson and T. 1. Meyer, I. Arn. Chern. Soc. 103, 5577 (1981).
84. M. J. Ridd and F. R. Keene, I. Arn. Chern. Soc. 103, 5733 (1981).
85. D. E. Cabelli and B. H. J. Bielski, I. Phys. Chern. 86, 2072 (1982).
86. E. C. Constable and K. R. Seddon, I. Chern. Soc., Chern. Cornrnun., 34 (1982).
87. A. Basu, M. A. Weiner, T. C. Strekas, and H. D. Gafney, [norg. Chern. 21,1085 (1982).
88. P. J. Wagner and R. Bartoszek-Loza, I. Arn. Chern. Soc. 103, 5587 (1981).
89. G. Giro, P. G. Di Marco, and G. Casalbore, [norg. Chirn. Acta 50,201 (1981).
90. R. F. Jones and D. J. Cole-Hamilton, [norg. Chirn. Acta 53, L3 (1981).
91. J. M. Clear, J. M. Kelly, C. M. O'Connell, and J. G. Vos, I. Chern. Res. (S), 260, (M),
3039 (1981).
92. R. S. Vagg and P. A. Williams, [norg. Chirn. Acta 51,61 (1981).
93. R. S. Vagg and P. A. Williams, [norg. Chirn. Acta 52,69 (1981).
94. B. P. Sullivan and T. J. Meyer, [norg. Chern. 21,1037 (1982).
95. R. Parashad, S. K. S. Yadav, and U. Agarwala, I. [norg. Nucl. Chern. 43, 2359 (1981).
96. S. Kohata and A. Ohyoshi, [norg. Chirn. Acta 64, U19 (1982).
97. c. K. Poon, T. C. Lau, and C. M. Che, I. Chern. Soc., Dalton Trans., 531 (1982).
98. J. D. Petersen, [norg. Chern. 20, 3123 (1981).
99. A. Vogler and H. Kunkely, [norg. Chirn. Acta 53, L215 (1981).
100. M. E. Kastner, K. F. Coffey, M. J. Clarke, S. E. Edmonds, and K. Eriks, I. Arn. Chern.
Soc. 103, 5747 (1981).
101. N. A. Ezerskaya, T. P. Solovykh, Ya. V. Salyn', and L. K. Shubochkin, Russ. I. [norg.
Chern. 26, 378 (1981).
102. S. C. Pati and M. Panda, Bull. Soc. Chirn. Belges 91, 271 (1982).
103. M. Itabashi, K. Shoji, and K. Itoh, Chern. Lett., 491 (1981).
104. J. E. Earley and T. FeaIey, [norg. Chern. 12, 323 (1973).
105. L. P. Bignetti, P. Chalilpoyil, and J. E. Earley, I. [norg. Nucl. Chern. 43,190 (1981).
106. Yann Hung, Wei-Jen Kung, and H. Taube, [norg. Chern. 20, 457 (1981).
107. G. H. Allen, B. P. Sullivan, and T. J. Meyer, I. Chern. Soc., Chern. Cornrnun., 793 (1981).
108. W. Preetz and H.-D. Zerbe, Z. Anorg. Allg. Chern. 479, 7 (1981).
109. H.-D. Zerbe and W. Preetz, Z. Anorg. AUg. Chern. 479,17 (1981).
110. H.-D. Zerbe and W. Preetz, Z. Anorg. Allg. Chern. 484, 33 (1982).
111. C. Bremard and B. Mouchel, [norg. Chern. 21, 1810 (1982).
112. M. J. Blandamer, J. Burgess, S. J. Hamshere, R. D. Peacock, J. H. Rogers, and H. D.
B. Jenkins, I. Chern. Soc., Dalton Trans., 726 (1981).
113. S. Bait and A. Jelsma,J. [norg. Nucl. Chern. 43,1287 (1981).
114. M. J. Saliby, E. B. Kaplan, P. S. Sheridan, and S. K. Madan, [norg. Chern. 20, 728 (1981).
115. A. J. Thirst and D. H. Vaughan, I. [norg. Nucl. Chern. 43, 2889 (1981).
116. S. Bait and A. Jelsma, [norg. Chern. 20,733 (1981).
117. S. BaIt and A. Jelsma, Transition Met. Chern. 6,119 (1981).
118. W. Weber, D. A. Palmer, and H. KeIrn, [norg. Chern. 21, 1689 (1982).
119. S. F. Chan and G. M. Harris, [norg. Chern. 18, 718 (1979).
120. K. E. Hyde, H. KeIrn, and D. A. Palmer, [norg. Chern. 17, 1647 (1978).
121. W. Weber, D. A. Palmer, and H. KeIrn, [norg. Chirn. Acta 54, U77 (1981).
122. J. L. Armstrong, M. J. Blandamer, J. Burgess, and A. Chew, I. [norg. Nucl. Chern. 43,
173 (1981).
123. C. Chatterjee and A. S. Bali, I. Coord. Chern. 11, 179 (1981).
124. S. Bait and A. Jelsma, I. Chern. Soc., Dalton Trans., 1289 (1981).
125. O. W. Howarth, C. H. McAteer, P. Moore, and G. E. Morris, I. Chern. Soc., Dalton
Trans., 1481 (1981).
402 References
126. A. P. Kochetkova, L. B. Sveshnikova, V. M. Stepanovich, and I. Z. Babievskaya, Russ.
J. [norg. Chem. 26, 1340 (1981).
127. A. Peloso, J. Chem. Soc., Dalton Trans., 2429 (1981).
128. M. Larson, H. Macke, R. C. Rumfeldt, and A. W. Adamson, [norg. Chim. Acta 57,
229 (1982).
129. D. A. Sexton, L. H. Skibsted, D. Magde, and P. C. Ford, I. Phys. Chem. 86,1758 (1982).
130. M. A. Bergkamp, R. J. Watts, and P. C. Ford, J. Phys. Chem. 85, 684 (1981).
131. L. G. Vanquickenborne and A. Ceulemans, [norg. Chem. 20,110 (1981).
132. S. F. Clark and 1. D. Petersen, [norg. Chem. 20, 280 (1981).
133. P. C. Ford, Coord. Chem. Rev. 44, 61 (1982).
134. R. D. Cannon, D. B. Powell, and K. Sarawek, [norg. Chem. 20, 1470 (1981).
135. R. S. Drago, J. R. Long, and R. Cosmano, [norg. Chem. 20, 2920 (1981).
136. F. Galsbllli and B. S. Rasmussen, Acta Chem. Scand. 36A, 439 (1982).
137. W. A. Wickramasinghe, P. H. Bird, and N. Serpone, J. Chem. Soc., Chem. Commun.,
1284 (1981).
138. P. J. Spellane and R. J. Watts, [norg. Chem. 20, 3561 (1981).
139. R. J. Watts, [norg. Chem. 20,2302 (1981).
140. Y. Ohashi, Bull. Chem. Soc. Japan 54,3673 (1981).
141. R. I. Haines and A. McAuley, Coord. Chem. Rev. 39, 77 (1981).
142. T. K. Kazbanova and G. D. Mal'chikov, Russ. J. [norg. Chem. 26, 540 (1981).
143. R. D. Gillard and R. J. Wademan, J. Chem. Soc., Chem. Commun., 448 (1981).
144. O. Mlllnsted and G. Nord, J. Chem. Soc., Dalton Trans., 2599 (1981).
145. R. D. Gillard and R. J. Wademan, J. Chem. Soc., Dalton Trans., 2599 (1981).
146. M. Chan on and M. L. Tobe, Angew. Chem. Int. Ed. 21, 1 (1982).
147. F. G. Riddell, R. D. Gillard, and F. L. Wimmer, J. Chem. Soc., Chem. Commun. 333
(1982).
148. E. W. Abel, S. K. Bhargava, K. Kite, K. G. Orrell, V. Sik, and B. L. Williams, J. Chem.
149. E. W. Abel, M. Booth, G. King, K. G. Orrell, G. M. Pring, and V. Sik, J. Chem. Soc.,
150. E. W. Abel, M. Booth, K. G. Orrell, and G. M. Pring, J. Chem. Soc., Dalton Trans.,
1944 (1981).
1. D. L. Pisaniello, S. F. Lincoln, and T. Kurucsev, Aust. J. Chem. 35, 839 (1982).
2. M. Tanaka, [norg. Chim. Acta 54, L129 (1981).
3. M. J. Sisley, Y. Yano, and T. W. Swaddle, [norg. Chem. 21, 1141 (1982).
4. S. F. Lincoln and M. N. Tkaczuk, Ber. Bunsenges. Phys. Chem. 85, 433 (1981).
5. M. N. Tkaczuk and S. F. Lincoln, Ber. Bunsenges. Phys. Chem. 86, 147 (1982).
6. S. F. Lincoln and M. N. Tkaczuk, Ber. Bunsenges. Phys. Chem. 86, 221 (1982).
7. H. Strehlow, D. H. Devia, S. Dagnall, and G. Busse, Ber. Bunsenges. Phys. Chem. 85,
281 (1981).
8. S. F. Lincoln, D. L. Pisaniello, T. M. Spotswood, and M. N. Tkaczuk, Aust. J. Chem.
34,283 (1981).
9. A. Monnerat, P. Moore, K. E. Newman, and A. E. Merbach, [norg. Chim. Acta 47,
139 (1981).
10. S. Sattar and D. Eden, J. Phys. Chem. 86, 140 (1982).
11. H. B. Silber, L. U. Kromer, and F. Gaizer, [norg. Chem. 20, 3323 (1981).
12. S. Yamada and R. E. Verrall, 1. Phys. Chern. 85, 3145 (1981).
13. D. L. Pisaniello and S. F. Lincoln, Inorg. Chern. 20, 3689 (1981).
14. M. Grant and R. B. Jordan, Inorg. Chern. 20, 55 (1981).
15. T. W. Swaddle and A. E. Merbach, Inorg. Chern. 20,4212 (1981).
16. H. W. Dodgen, G. Liu, and J. P. Hunt, Inorg. Chern. 20, 1002 (1981).
17. F. K. Meyer, A. R. Monnerat, K. E. Newman, and A. E. Merbach, Inorg. Chern. 21,
774 (1982).
18. E. Mentasti, F. Secco, and M. Venturini, Inorg. Chern. 21, 2314 (1982).
19. A. C. Dash and G. M. Harris, Inorg. Chern. 21,1265 (1982).
20. A. C. Dash and G. M. Harris, Inorg. Chern. 21, 2336 (1982).
21. H. H. Trimm, H. Ushio, and R. C. Patel, Talanta 28,753 (1981).
22. D. L. Pisaniello and S. F. Lincoln, Aust. 1. Chern. 34,1195 (1981).
23. D. L. Pisaniello, S. F. Lincoln, E. H. Williams, and A. J. Jones, Aust. 1. Chern. 34, 495
(1981).
24. D. L. Pisaniello and A. E. Merbach, Helv. Chirn. Acta 65, 573 (1982).
25. A. M. Hounslow, S. F. Lincoln, P. A. Marshall, and E. H. Williams, Aust. 1. Chern.
34,2543 (1981).
26. B. G. Cox, J. Garcia-Rosas, and H. Schneider, Ber. Bunsenges. Phys. Chern. 86, 293
(1982).
27. B. G. Cox, J. Garcia-Rosas, and H. Schneider, 1. Phys. Chern. 84, 3178 (1980).
28. B. G. Cox, P. Firman, I. Schneider, and H. Schneider, Inorg. Chirn. Acta 49, 153 (1981).
29. B. G. Cox, J. Garcia-Rosas, and H. Schneider, 1. Arn. Chern. Soc. 103, 1054 (1981).
30. B. G. Cox, W. Jedral, P. Firman, and H. Schneider, 1. Chern. Soc., Perkin Trans. 2,
1486 (1981).
31. B. G. Cox, J. Garcia-Rosas, and H. Schneider, 1. Arn. Chern. Soc. 104, 2434 (1982).
32. H. Farber and S. Petrucci, 1. Phys. Chern. 85, 1396 (1981).
33. 1. K. Beattie and M. T. Kelso, Aust. 1. Chern. 34, 2563 (1981).
34. G. W. Liesegang, 1. Arn. Chern. Soc. 103,953 (1981).
35. B. G. Cox, P. Firman, and H. Schneider, Inorg. Chirn. Acta 64, L263 (1982).
36. A. Nagasawa and H. Diebler, 1. Phys. Chern. 85, 3523 (1981).
37. T. M. Che and K. Kustin, Inorg. Chern. 20, 509 (1981).
38. R. B. Jordan, 1. Coord. Chern. 10, 239 (1980).
39. T. Inoue, K. Kojima, and R. Shimozawa, Chern. Lett. 259 (1981): Chern. Abs. 94,
109927z (1981).
40. K. Tamura, S. Harada, Y. Funaki, and T. Yasunaga, Bull. Chern. Soc. Japan 55,813
(1982).
41. R. A. Read and D. W. Margerum, [norg. Chern. 20, 3143 (1981).
42. C. E. Bannister and D. W. Margerum, Inorg. Chern. 20, 3149 (1981).
43. c. E. Bannister, J. M. T. Raycheba, and D. W. Margerum,lnorg. Chern. 21,1106 (1982).
44. D. Banerjea, Trans. Met. Chern. 7, 22 (1982); Chern. Abs. 96, 130515q (1982).
45. J. R. Hicks and V. C. Reinsborough, Aust. 1. Chern. 35, 15 (1982).
46. P. D. I. Fletcher and V. C. Reinsborough, Can. 1. Chern. 59, 1361 (1981).
47. C. Tondre, 1. Chern. Soc., Faraday Trans. 178,1795 (1982).
48. N. Sbiti and C. Tondre, 1. Chern. Soc., Faraday Trans. 1 78, 1809 (1982).
49. E. F. Caldin and R. C. Greenwood, 1. Chern. Soc., Faraday Trans. 1 77, 773 (1981).
50. c. N. Elgy and C. F. Wells, 1. Chern. Soc., Faraday Trans. 1 77,2529 (1981).
51. J. Brauner, D. Saar,-and P. Hemmes, Adv. Mol. Relaxation Interact. Processes 20, 249
(1981).
52. D. Pacheco A., F. Creazzola de 0., J. A. Sequera B., J. D. Medina, and V. de San tis
de M., Int. 1. Chern. Kinet. 14, 599 (1982).
404 References
53. L. Hertli and T. A. Kaden, Helv. Chirn. Acta 64,33 (1981).
56. A. Kumar, J. Phys. Chern. 86, 1674 (1982).
57. B. G. Cox, P. Firman, and H. Schneider, Inorg. Chern. 21,2320 (1982).
58. T. J. Kemp, P. A. Lampe, P. Moore, and G. R. Quick, J. Chern. Soc., Dalton Trans.,
2137 (1981).
59. E. Mentasti, J. Chern. Soc., Dalton Trans., 721 (1982).
60. J. Sachinidis and M. W. Grant, Aust. J. Chern. 34, 2195 (1981).
61. C. Baiocchi and E. Mentasti, Ann. Chirn. (Rome) 71, 631, (1981); Chern. Abs. 96,
41636n (1982).
62. M. Hiraishi, J. Sci. Hiroshima Univ. Ser. A: Phys. Chern. 44, 311 (1980); Chern. Abs.
94, 72234t (1981).
63. P. N. Mathur and H. Fukutomi, J. Inorg. Nucl. Chern. 43, 2869 (1981).
64. B. Perlmutter-Hayman and E. Tapuhi, J. Coord. Chern. 10, 219 (1980).
65. E. Mentasti, F. Secco, and M. Venturini, Inorg. Chern. 21, 602 (1982).
66. F. P. Cavasino, E. DiDio, and C. Sbriziolo, J. Chern. Soc., Dalton Trans., 2414 (1981).
67. N. M. Novikova and V. T. Novikov, Zh. Neorg. Khirn. 26, 1413 (1981); Chern. Abs.
95, 13512e (1981).
68. E. Mentasti and C. Baiocchio, J. Coord. Chern. 10, 229 (1980).
69. M. S. EI-Ezaby and A. S. I. Abu-Shady, Inorg. Chirn. Acta 55,29 (1981).
70. G. Krishnamoorthy and B. S. Prabhanada, J. Inorg. Nucl. Chern. 43,1267 (1981).
71. K. Nakano, Y. Narusawa, and M. Tsuchiya, J. Inorg. Nucl. Chern. 43, 3011 (1981).
72. K. Nakano, Y. Narusawa, and H. Moroi, Bull. Chern. Soc. Japan 54,2529 (1981).
73. B. Henry, J. C. Boubel, and J. J. Delpuech, Polyhedron 1, 113 (1982).
74. D. Littlejohn and S. G. Chang, J. Phys. Chern. 86, 537 (1982).
75. J. M. Malin, B. S. Brunschwig, G. M. Brown, and K. S. Kwan, Inorg. Chern. 20, 1438
(1981).
76. D. H. Macartney and A. McAuley, J. Chern. Soc., Dalton Trans., 1780 (1981).
77. R. K. Steinhaus and B. I. Lee, Inorg. Chern. 21, 1829 (1982).
78. D. Banerjea, T. A. Kaden, and H. Sigel, Inorg. Chirn. Acta 56, L53 (1981).
79. J. H. Coates, D. A. Hadi, S. F. Lincoln, H. W. Dodgen, and J. P. Hunt, Inorg. Chern.
20,707 (1981).
80. G. R. Cayley, I. D. Kelly, P. F. Knowles, and K. D. S. Yadav, J. Chern. Soc., Dalton
Trans., 2370 (1981).
81. I. NagypaJ, F. Debreczeni, and R. E. Connick, Inorg. Chirn. Acta 48, 225 (1981).
82. I. Nagypal, F. Debreczeni, and F. Erdodi, Inorg. Chirn. Acta 57, 125 (1982).
83. V. G. Shtyrlin, A. V. Zakharov, I. I. Evgen'eva, Z. A. Saprykova, Zh. Neorg. Khirn.
26,2986 (1981); Chern. Abs. 96, 12077a (1982).
84. F. Debreczeni and I. Nagypal, Inorg. Chirn. Acta 57, 135 (1982).
85. I. Nagypal and F. Debreczeni, Inorg. Chirn. Acta 58,207 (1982).
86. M. C. Gennaro and P. Mirti, J. Inorg. Nucl. Chern. 43,1711 (1981).
87. R. Van EJdik, D. A. Palmer, R. Schmidt, and H. Keirn, Inorg. Chirn. Acta 50, 131 (1981).
88. C. G. Ekstrom, N. Nilsson, and I. Grenthe, Inorg. Chirn. Acta 48, 145 (1981).
89. Y. Ikeda, S. Soya, H. Tomiyasu, and H. Fukutomi, Bull. Chern. Soc. Japan 54,3768
(1981).
90. S. A. Kazmi and J. V. McArdle, J. Inorg. Nucl. Chern. 43, 3031 (1981).
91. S. Funahashi, M. Inamo, K. Ishihara, and M. Tanaka, Inorg. Chern. 21, 447 (1982).
92. O. Yokoyama, H. Tomiyasu, and G. Gordon, Inorg. Chern. 21, 1136 (1982).
93. S. Funahashi, K. Ishihara, and M. Tanaka, Inorg. Chern. 20, 51 (1981).
94. J. Lagrange, K. Aka, and P. Lagrange, Inorg. Chem. 21,130 (1982).
95. C. Ercolani, F. Monacelli, G. Pennesi, G. Rossi, E. Antonini, P. Ascenzi, and M.
Brunori, J. Chem. Soc., Dalton Trans., 1120 (1981).
96. S. Yoshihiro, Chem. Lett., 1117 (1981); Chem. Abs. 95, 192990d (1981).
97. B. Ward, C. B. Wang, and C. K. Chang, J. Am. Chem. Soc. 103,5236 (1981).
98. 1. H. Cameron, A. G. Lappin, J. M. Winfield, and A. McAuley, J. Chem. Soc., Dalton
Trans., 2172 (1981).
99. F. L. Dickert and S. W. Hellmann, Ber. Bunsenges. Phys. Chem. 86, 153 (1982).
100. F. L. Dickert and S. W. Hellmann, Ber. Bunsenges. Phys. Chem. 85, 270 (1981).
101. A. Yamagishi, T. Masui, and F. Watanabe, lnorg. Chem. 20, 513 (1981).
102. Z. Dokuzovic, X. Ahmeti, D. Pavolovic, I. Murati, and S. Asperger, lnorg. Chem. 21,
1576 (1982).
103. M. Schumann, A. von Holtum, K. J. Wannowius, and H. Elias, lnorg. Chem. 21, 606
(1982).
104. H. Elias, H. Muth, B. Niedernhofer, and K. J. Wannowius, J. Chem. Soc., Dalton Trans.,
1825 (1981).
105. H. Elias, U. Frohn, G. Giegerich, M. Stenger, and K. J. Wannowius, J. Chem. Soc.,
106. H. Elias, U. ReiHer, M. Schumann, and K. J. Wannowius, lnorg. Chim. Acta 53, L65
(1981).
107. E. F. Caldin and J. P. Field, J. Chem. Soc., Faraday Trans. 1,78, 1923 (1982).
108. M. M. DoeH and D. A. Sweigart,lnorg. Chem. 20, 1683 (1981).
109. C. E. Holloway, D. V. Stynes, and C. P. J. Vuik, J. Chem. Soc., Dalton Trans., 95 (1982).
110. M. Cusumano, G. Guglielmo, and V. Ricevuto, J. Chem. Soc., Dalton Trans., 1722
(1981).
111. P. O'Brien and D. A. Sweigart, lnorg. Chem. 21, 2094 (1982).
112. Y. Ito and S. Kawaguchi, Bull. Chem. Soc. Japan 54, 150 (1981).
113. C. D. Baer, J. O. Edwards, and P. H. Rieger, lnorg. Chem. 20, 905 (1981).
114. J. J. Delpuech, A. Peguy, P. Rubini, and J. Steinmetz, Nouv. J. Chim. 1, 133 (1977).
115. 1. Crea and S. F. Lincoln, J. Chem. Soc., Dalton Trans., 2057 (1973).
1. F. Basolo, lnorg. Chim. Acta 50,65 (1981).
2. F. Basolo, Coord. Chem. Rev. 43, 7 (1982).
3. B. F. G. Johnson and J. Lewis, Adv.lnorg. Chem. Radiochem. 24, 225 (1981).
4. G. J. Bezems, P. H. Rieger, and S. Visco, J. Chem. Soc., Chem. Commun., 265 (1981).
5. D. P. Summers, J. C. Luong, and M. S. Wrighton, J. Am. Chem. Soc. 103, 5238 (1981).
6. J. W. Hershberger and J. K. Kochi, J. Chem. Soc., Chem. Commun., 212 (1982).
7. J. W. Hershberger, R. J. Klingler, and J. K. Kochi, J. Am. Chem. Soc. 104, 3034 (1982).
8. R. G. Pearson, H. W. Walker, H. Mauermann, and P. C. Ford, lnorg. Chem. 20, 2743
(1981).
9. F. Naumann and D. Rehder, J. Organomet. Chem. 204, 411 (1981).
10. W. D. Jones, J. M. Huggins, and R. G. Bergman, J. Am. Chem. Soc. 103,4415 (1981).
11. F. A. Cotton, D. J. Darensbourg, and B. W. S. Kolthammer, J. Am. Chem. Soc. 103,
398 (1981).
12. F. A. Cotton, D. J. Darensbourg, B. W. S. Kolthammer, and R. Kudaroski, lnorg.
Chem. 21, 1656 (1982).
13. D. J. Darensbourg, M. Y. Darensbourg, and N. Walker, lnorg. Chem. 20, 1918 (1981).
406 References
14. J. D. Atwood and T. L. Brown, 1. Am. Chern. Soc. 98, 3160 (1976).
15. D. J. Darensbourg, 1. Organornet. Chern. 209, C37 (1981).
16. G. R. Dobson and K. J. Asali, Inorg. Chern. 20, 3563 (1981).
17. C. P. Casey and M. C. Cesa, Organornetallics 1, 87 (1982).
18. H. Fischer, J. Muhlemeier, R. Markl, and K. H. Dotz, Chern. Ber. 115, 1355 (1982).
19. H. Fischer and A. Motsch, 1. Organornet. Chern. 220, 301 (1981).
20. J. Grobe and H. Zimmermann, Z. Naturforsch. 36b, 301, 482 (1981).
21. A. J. Lees and A. W. Adamson, Inorg. Chern. 20,4381 (1981).
22. K. A. Mahmoud, R. Narayanaswamy, and A. J. Rest, 1. Chern. Soc., Dalton Trans.,
2199 (1981).
23. M. Y. Darensbourg, P. Jimenez, J. A. Sackett, J. M. Hanckel, and R. L. Kump, 1. Am.
Chern. Soc. 104, 1521 (1982).
24. c. P. Casey, W. D. Jones, and S. G. Harsy, 1. Organornet. Chern. 206, C38 (1981).
25. R. L. Kump and L. J. Todd, Inorg. Chern. 20, 3715 (1981).
26. N. J. Coville, 1. Organornet. Chern. 218, 337 (1981).
27. M. O. Albers, N. J. Coville, and E. Singleton, 1. Chern. Soc., Dalton Trans., 1069 (1982).
28. M. O. Albers, N. J. Coville, T. V. Ashworth, and E. Singleton, 1. Organornet. Chern.
217,385 (1981).
29. M. O. Albers, N. J. Coville, and E. Singleton, 1. Organornet. Chern. 232, 261 (1982).
30. N. J. Coville, M. O. Albers, T. V. Ashworth, and E. Singleton, 1. Chern. Soc., Chern.
Cornrnun., 408 (1981).
31. c.-Y. Chang, C. E. Johnson, T. G. Richmond, Y.-T. Chen, W. C. Trogler, and F.
Basolo, Inorg. Chern. 20, 3167 (1981).
32. C. E. Johnson and W. C. Trogler, 1. Am. Chern. Soc. 103,6352 (1981).
33. R. J. Kazlauskas and M. S. Wrighton, Organornetallics 1,602 (1982).
34. K. Tabatabaian and C. White, Inorg. Chern. 20, 2020 (1981).
35. P. B. Brindley and M. J. Scotton, I. Organornet. Chern. 222, 89 (1981).
36. M. Y. Darensbourg and J. M. Hanckel, Organornetallics 1, 82 (1982).
37. D. J. Darensbourg and J. A. Ewen, Inorg. Chern. 20, 4168 (1981).
38. F. A. Cotton, D. J. Darensbourg, S. Klein, and B. W. S. Kolthammer, Inorg. Chern.
21,1651 (1982).
39. D. J. Darensbourg, R. Kudaroski, and W. Schenk, Inorg. Chern. 21, 2488 (1982).
40. W. A. Shenk and H. Muller, Inorg. Chern. 20, 6 (1981).
41. G. R. Dobson, Z. Y. Al-Saigh, and N. S. Binzet, I. Coord. Chern. 11, 159 (1981).
42. M. J. Blandamer, J. Burgess, J. G. Chambers, and A. J. Duffield, Trans. Met. Chern.
6, 156 (1981).
43. S. M. B. Costa, A. R. Dias, and F. J. S. Pina, I. Organornet. Chern. 217, 357 (1981).
44. H. Ogino, M. Shimura, and N. Tanaka, Inorg. Chern. 21, 126 (1982).
45. A. Bakac, J. H. Espenson, and L. P. Miller, Inorg. Chern. 21, 1557 (1982).
47. B. M. Mattson and W. A. G. Graham, Inorg. Chern. 20, 3186 (1981).
48. G. Bellachioma and G. Cardaci, 1. Organornet. Chern. 205, 91 (1981).
49. C. M. Carr, D. M. Davies, M. Gower, L. A. P. Kane-Maguire, and D. A. Sweigart, 1.
50. M. Stephenson and R. J. Mawby, I. Chern. Soc., Dalton Trans., 2112 (1981).
51. T. V. Ashworth, D. J. A. de Waal, and E. Singleton, I. Chern. Soc., Chern. Cornrnun.,
78 (1981).
52. S. Torroni, G. Innorta, A. Foffani, A. Modelli, and F. Scagnolari, I. Organornet. Chern.
221,309 (1981).
53. A. H. Janowicz, H. E. Bryndza, and R. G. Bergman, I. Am. Chern. Soc. 103, 1516 (1981).
407
54. O. W. Howarth, C. H. McAteer, P. Moore, and G. E. Morris, J. Chern. Soc., Dalton
Trans., 1481 (1981).
55. A. C. Sievert and E. L. Muetterties, Inorg. Chern. 20,489 (1981).
56. E. K. Barefield, D. A. Krost, D. S. Edwards, D. G. Van Derveer, R. L. Try tko, and
S. P. O'Rear, J. Am. Chern. Soc. 103,6219 (1981).
57. N. Chaudhury and R. J. Puddephatt, Inorg. Chern. 20, 467 (1981).
58. H. van der Poel, G. van Koten, and G. C. van Stein, J. Chern. Soc., Dalton Trans.,
2164 (1981).
59. M. I. Bruce, D. C. Kehoe, J. G. Matisons, B. K. Nicholson, P. H. Rieger, and M. L.
Williams, J. Chern. Soc., Chern. Cornrnun., 442 (1982).
60. c. M. Arewgoda, B. H. Robinson, and J. Simpson, J. Chern. Soc., Chern. Cornrnun.,
284 (1982).
61. S. Amer, G. Kramer, and A. Poe, J. Organornet. Chern. 209, C28 (1981).
62. S. Amer and A. Poe, J. Organornet. Chern. 209, C31 (1981).
63. G. S. Girolami, V. V. Mainz, R. A. Andersen, S. H. Vollmer, and V. W. Day, J. Am.
Chern. Soc. 103, 3953 (1981).
64. R. W. Wegman, R. J. Olsen, D. R. Gard, L. R. Faulkner, and T. L. Brown, J. Am.
Chern. Soc. 103, 6089 (1981).
65. W. K. Meckstroth, R. T. Walters, W. L. Waltz, A. Wojcicki, and L. M. Dorfman, 1.
Am. Chern. Soc. 104, 1842 (1982).
66. B. H. Byers and T. L. Brown, J. Am. Chern. Soc. 99, 2527 (1977).
67. T. L. Brown, Ann. N. Y. Acad. Sci. 333, 80 (1980).
68. S. B. McCullen, H. W. Walker, and T. L. Brown, J. Am. Chern. Soc. 104,4007 (1982).
69. A. Fox, J. Malito, and A. Poe, J. Chern. Soc., Chern. Cornrnun., 1052 (1981).
70. A. Poe, Trans. Met. Chern. 7, 65 (1982).
71. Q.-Z. Shi, T. G. Richmond, W. C. Trogler, and F. Basolo, J. Am. Chern. Soc. 104,
4032 (1982).
72. D. Sonnenberger and J. D. Atwood, J. Am. Chern. Soc. 102, 3484 (1980).
73. A. Poe, Inorg. Chern. 20,4029,4033 (1981).
74. J. D. Atwood, Inorg. Chern. 20, 4031 (1981).
75. S. P. Schmidt, W. C. Trogler, and F. Basolo, Inorg. Chern. 21, 1699 (1982).
76. R. A. Jackson, R. Kanluen, and A. Poe, Inorg. Chern. 20, 1130 (1981).
77. J. R. Fox, W. L. Gladfelter, T. G. Wood, J. A. Smegal, T. K. Foreman, G. L. Geoffroy,
I. Tavanaiepour, V. W. Day, and C. S. Day, Inorg. Chern. 20, 3214 (1981).
78. H. C. Foley and G. L. Geoffroy, J. Am. Chern. Soc. 103, 7176 (1981).
79. D. A. Roberts, W. C. Mercer, S. M. Zahurak, G. L. Geoffroy, C. W. DeBrosse, M. E.
Cass, and C. G. Pierpont, J. Am. Chern. Soc. 104, 910 (1982).
80. R. Hug and A. Poe, J. Organornet. Chern. 226, 277 (1982).
81. D. J. Darensbourg, B. S. Peterson, and R. E. Schmidt, Organornetallics 1, 306 (1982).
82. D. J. Darensbourg and M. 1. Incorvia, Inorg. Chern. 20,1911 (1981).
83. K. J. Karel and J. R. Norton, J. Am. Chern. Soc. 96, 6812 (1974).
84. D.1. Darensbourg and B. J. Baldwin-Zuschke, J. Am. Chern. Soc. 104, 3906 (1982).
85. D. J. Darensbourg and B. J. Baldwin-Zuschke, Inorg. Chern. 20, 3846 (1981).
86. G. F. Struntz and J. R. Shapley, 1. Organornet. Chern. 213, 389 (1981).
87. D. Sonnenberger and J. D. Atwood, Inorg. Chern. 20, 3243 (1981).
88. D. C. Sonnenberger and J. D. Atwood, J. Am. Chern. Soc. 104, 2113 (1982).
89. D. C. Sonnenberger and J. D. Atwood, Organornetallics 1,694 (1982).
90. J. D. Cotton, G. T. Crisp, and V. A. Daly, Inorg. Chirn. Acta 47, 165 (1981).
91. M. J. Wax and R. G. Bergman, J. Am. Chern. Soc. 103, 7028 (1981).
92. T. c. Flood, J. E. Jensen, and J. A. Statler, J. Am. Chern. Soc. 103,4410 (1981).
408 References
93. S. B. Butts, S. H. Strauss, E. M. Holt, R. E. Stimson, N. W. Alcock, and D. F. Shriver,
f. Arn. Chern. Soc. 102, 5093 (1980).
94. T. G. Richmond, F. Basolo, and D. F. Shriver, Inorg. Chern. 21,1272 (1982).
95. S. B. Butts, T. G. Richmond, and D. F. Shriver, Inorg. Chern. 20, 278 (1981).
96. K. R. Grundy and W. R. Roper, f. Organornet. Chern. 216, 255 (1981).
97. S. J. LaCroce and A. R. Cutler, 1. Arn. Chern. Soc. 104, 2312 (1982).
98. K. Nicholas, S. Raghu, and M. Rosenblum, 1. Organornet. Chern. 78, 133 (1974).
99. J. D. Cotton, G. T. Crisp, and L. Latif, Inorg. Chirn. Acta 47, 171 (1981).
100. H. Brunner and H. Vogt, Angew. Chern. Int. Ed. Engl. 20,405 (1981).
101. H. Brunner and H. Vogt. Chern. Ber. 114, 2186 (1981).
102. S. Quinn, A. Shaver, and V. W. Day, 1. Arn. Chern. Soc. 104, 1096 (1982).
103. c. R. Jablonski, Inorg. Chern. 20, 3940 (1981).
104. M. A. Bennett, J. C. Jeffrey, and G. B. Robertson, Inorg. Chern. 20, 323 (1981).
105. G. K. Anderson, H. C. Clark, and 1. A. Davies, Organornetallics 1,64 (1982).
106. R. J. Cross and J. Gemmill, 1. Chern. Soc., Dalton Trans., 2317 (1981).
107. J. P. Collman, R. K. Rothrock, R. G. Finke, E. J. Moore, and F. Rose-Munch, Inorg.
Chern. 21, 146 (1982).
108. A. Dedieu, Inorg. Chern. 20, 2803 (1981).
109. J. M. Huggins and R. G. Bergman,l. Arn. Chern. Soc. 103, 3002 (1981).
110. B. L. Booth and E. J. R Lewis, 1. Chern. Soc., Dalton Trans., 417 (1982).
111. R. S. Threlkel and J. E. Bercaw, 1. Arn. Chern. Soc. 103, 2650 (1981).
112. R. R. Ryan, G. J. Kubas, D. C. Moody, and P. G. Eller, Struct. Bond. 46, 47 (1981).
113. W. Dell and M. L. Ziegler, Angew. Chern. Int. Ed. Engl. 20, 471 (1981).
114. W. Dell and M. L. Ziegler, Z. Naturforsch. 37b, 1 (1982).
115. W. P. Weiner, M. A. White, and R. G. Bergman, 1. Arn. Chern. Soc. 103, 3612 (1981).
116. H. Fischer, 1. Organornet. Chern. 222, 241 (1981).
1. J. Halpern, Inorg. Chirn. Acta 50, 11 (1981).
2. P. J. Brothers, Prog. Inorg. Chern. 28,1 (1981).
3. F. Jardine, Prog. Inorg. Chern. 28, 63 (1981).
4. D. A. Ryan and J. H. Espenson, 1. Arn. Chern. Soc. 104,704 (1982).
5. G. W. Kirker, A. Bakac, and J. H. Espenson, 1. Arn. Chern. Soc. 104, 1249 (1982).
6. V. Gold and D. L. Wood, 1. Chern. Soc., Dalton Trans., 2462 (1981).
7. H. Ogino, M. Shimura, and N. Tanaka, Inorg. Chern. 21,126 (1982).
8. A. Petrou, E. Vrachnou-Astra, J. Konstantatos, N. Katsaros, and D. Katakis, Inorg.
Chern. 20, 1091 (1981).
10. A. Bakac and J. H. Espenson, 1. Arn. Chern. Soc. 103, 2721 (1981).
11. A. Bakac and J. H. Espenson, Inorg. Chern. 20, 1621 (1981).
12. J. H. Espenson and A. Bakac, 1. Arn. Chern. Soc. 103, 2728 (1981).
13. L. A. Funke and J. H. Espenson, Inorg. Chern. 20, 897 (1981).
14. T.-T. Tsou, M. Loots, and J. Halpern, 1. Arn. Chern. Soc. 104,623 (1982).
15. H. B. Gjerde and J. H. Espenson, Organornetallics 1,435 (1982).
16. F. T. T. Ng, G. L. Rempel, and J. Halpern, 1. Arn. Chern. Soc. 104, 621 (1982).
17. G. N. Schrauzer and J. H. Grate, 1. Arn. Chern. Soc. 103,541 (1981).
18. J. H. Grate, J. W. Grate, and G. N. Schrauzer, 1. Arn. Chern. Soc. 104, 1588 (1982).
19. K. L. Brown, 1. Chern. Soc. Chern. Cornrnun., 598 (1981).
409
20. K. L. Brown and R. K. Hessley, Inorg. Chirn. Acta. 53, L115 (1981).
21. K. L. Brown and S. Ramamurthy, Organornetallics 1,413 (1982).
22. W. W. Reenstra, R. H. Abeles and W. P. Jencks, 1. Am. Chern. Soc., 104 (1982).
23. R. C. McHatton, J. H. Espenson, and A. Bakai:, 1. Am. Chern. Soc. 104, 3531 (1982).
24. Y.-T. Fanchiang and J. M. Wood, 1. Am. Chern. Soc. 103, 5100 (1981).
25. J. S. Thayer, Inorg. Chern. 20, 3573 (1981).
26. Y.-T. Fanchiang, Inorg. Chern. 21, 2344 (1982).
27. J. H. Dimmit and J. H. Weber, Inorg. Chern. 21, 700 and 1554 (1982).
28. W. H. Tamblyn, R. J. Klinger, W. S. Hwang, and J. K. Kochi, 1. Am. Chern. Soc. 103,
3161 (1981).
29. M. Hoshino, S. Konishi, Y. Terai, and M. Imamura, Inorg. Chern. 21, 89 (1982).
30. D. Dolphin, D. J. Halko, and E. Johnson, Inorg. Chern. 20,4348 (1981).
31. M. D. Le Hoang, Y. Robin, J. Devynck, C. Bied-Charreton, and A. Gaudemer, 1.
Organornet. Chern. 222, 311 (1981).
32. P. B. Armentrout and J. L. Beauchamp, 1. Am. Chern. Soc. 103,784 (1981).
33. P. B. Armentrout and J. L. Beauchamp, 1. Am. Chern. Soc. 103, 6628 (1981).
34. J. A. Marsella and K. G. Caulton, J. Am. Chern. Soc. 104,2361 (1982).
35. P. B. Brindley and M. S. Scotton, 1. Organornet. Chern. 222, 89 (1981).
36. M. Pankowski and E. Samuel, 1. Organornet. Chern. 221, C21 (1981).
37. D. Brault and P. Neta, 1. Am. Chern. Soc. 103, 2705 (1981).
38. D. Mansuy, M. Fontecave, and J.-P. Battioni, 1. Chern. Soc., Chern. Cornrnun., 317
(1982); see also, 1. Chern. Soc., Chern. Cornrnun., 638 (1982).
39. D. Lexa, J. Mispelter, and J.-M. Saveant, 1. Am. Chern. Soc. 103,6806 (1981).
40. W. N. Rogers, J. A. Page, and M. C. Baird, Inorg. Chern. 20, 3521 (1981).
41. D. W. Firsich and R. J. Lagow, 1. Chern. Soc., Chem. Cornrnun., 1283 (1981).
42. G. A. Russel, J. Herschberger, and K. Owens, 1. Organomet. Chern. 225, 43 (1982).
43. J. L. Wardell and 1. McM. Wigzell, 1. Organornet. Chern. 205, C24 (1981).
44. K. S. Root, J. Deutch, and G. M. Whitesides, 1. Am. Chern. Soc. 103, 5475 (1981).
45. G. Molle and P. Bauer, 1. Am. Chern. Soc. 104, 3481 (1982).
46. J. S. Uppal and R. H. Staley, 1. Am. Chem. Soc. 104, 1229 and 1238 (1982).
47. Y. Tanaka, S. C. Davis, and K. J. Klabunde, 1. Am. Chern. Soc. 104, 1013 (1982).
48. E. C. Ashby and R. S. Smith, J. Organornet. Chem. 225, 71 (1982).
49. G. M. Williams and J. Schwartz, 1. Am. Chern. Soc. 104, 1122 (1982).
50. K.1. Gell, B. Posin, G. Schwartz, and G. M. Williams,!. Am. Chern. Soc. 104, 1846 (1982).
51. M. Y. Darensbourg, P. Jimenez, J. R. Sackett, J. M. Hanckel, and R. L. Kump, J. Am.
Chem. Soc. 104, 1521 (1982).
52. M. J. Nappa, R. Santi, S. P. Diefenbach, and J. Halpern, 1. Am. Chem. Soc. 104, 619
(1982).
53. W. Lau, J. C. Huffmann, and J. K. Kochi, Organornetallics 1, 155 (1982).
54. G. Bellachioma, G. Cardaci and G. Reichenbach, 1. Organornet. Chern. 221, 291 (1981).
55. A. J. Blakeney and J. A. Gladysz, Inorg. Chim. Acta 53, L25 (1981).
56. M. I. Bruce, I. B. Tomkins, F. S. Wong, B. W. Skelton, and A. H. White, 1. Chern. Soc.,
57. A. H. Janowicz and R. G. Bergmann, 1. Am. Chern. Soc. 103, 2488 (1981).
58. M. B. Mooiman and J. M. Pratt, 1. Chern. Soc., Chem. Cornrnun., 33 (1981).
59. J. U. Mondal, R. Bulls, and D. M. Blake, Inorg. Chern. 21, 1668 (1982).
60. S. Franks, F. R. Hartley, and J. R. Chipperfield, Inorg. Chern. 20, 3238 (1981).
61. S. A-Jibori, C. Crocker, and B. L. Shaw, 1. Chem. Soc., Dalton Trans., 319 (1981).
62. A. Cuccuru, P. Diversi, G. Ingrosso, and A. Lucherini, J. Organomet. Chern. 204, 123
(1981).
410 References
63. J. A. Kampmeier, S. H. Harris, and R. M. Rodehorst, J. Am. Chem. Soc. 103, 1478
(1981).
64. D. J. A. de Waal, T. I. A. Gerber, and W. J. Louw, Inorg. Chem. 21, 1259 (1982).
65. D. J. A. de Waal, T. I. A. Gerber, W. J. Louw, and R. van Eldik, Inorg. Chem. 21,
2002 (1982).
66. D. J. A. de Waal, T. I. A. Gerber and W. J. Louw, J. Chem. Soc., Chem. Commun.,
100 (1982).
67. W. J. Louw, D. J. A. de Waal, T. I. A. Gerber, C. M. Demanet, and R. G. Copperthwaite,
Inorg. Chem. 21, 1667 (1982).
68. R. G. Pearson and C. T. Kresge, Inorg. Chem. 20, 1878 (1981).
69. E. F. Landvatter and T. B. Rauchfuss, Organometallics I, 506 (1982).
70. G. Yoneda and D. M. Blake, Inorg. Chem. 20, 67 (1981).
71. G. Yoneda, S.-M. Lin, L.-P. Wang, and D. M. Blake, J. Am. Chem. Soc. 103, 5768
(1981).
72. A. H. Janowicz and R. G. Bergmann, J. Am. Chem. Soc. 104, 352 (1982).
73. J. K. Hoyano and W. A. G. Graham, J. Am. Chem. Soc. 104, 3723 (1982).
74. D. Milstein and J. C. Calabrese, J. Am. Chem. Soc. 104, 3773 (1982).
75. B. L. Booth, R. N. Haszeldine, and R. G. G. Holmes, J. Chem. Soc., Dalton Trans.,
671 (1982).
76. K. Kitaura, S. Obara, and K. Morokuma, J. Am. Chem. Soc. 103, 2891 (1981).
77. K. Tatsumi, R. Hoffmann, A. Yakamoto, and J. K. Stille, Bull. Chem. Soc. Japan 54,
1857 (1981).
78. A. C. Balazs, K. H. Johnson, and G. M. Whitesides, Inorg. Chem. 21, 2162 (1982).
79. R. J. McKinney, D. L. Thorn, R. Hoffmann, and A. Stockis, J. Am. Chem. Soc. 103,
2585 (1981).
80. A. Morvillo and A. Turco, J. Organomet. Chem. 208, 103 (1981).
81. A. Morvillo and A. Turco, J. Organomet. Chem. 224, 387 (1982).
82. J.-F. Fauvarque, F. Pfliiger, and M. Troupel, J. Organomet. Chem. 208,419 (1981).
83. T. Yamamoto, O. Saito, and A. Yamamoto, J. Am. Chem. Soc. 103,5601 (1981).
84. F. Ozawa, T. Ito, Y. Nakamura, and A. Yamamoto, Bull. Chem. Soc. Japan 54, 1868
(1981).
85. A. Morarskiy and J. K. Stille, J. Am. Chem. Soc. 103, 4182 (1981).
86. M. K. Loar and J. K. Stille, J. Am. Chem. Soc. 103,4174 (1981).
87. S. Franks and F. R. Hartley, Inorg. Chim. Acta 49,227, (1981).
88. C. Eaborn, K. Kundu, and A. Pidcock, J. Chem. Soc., Dalton Trans., 1223, (1981); see
also T. A. K. AI-Allaf, C. Eaborn, K. Kundu, and A. Pidcock, J. Chem. Soc., Chem.
Commun., 55 (1981).
89. J. W. Gosselink, G. V. Koten, A. M. F. Brouwers, and O. Overbeck, J. Chem. Soc.,
90. R. Di Cosimo, S. S. Moore, A. F. Sowinski, and G. M. Whitesides, J. Am. Chem. Soc.
104, 124 (1982).
91. R. Di Cosimo and G. M. Whitesides, J. Am. Chem. Soc. 104,3601 (1982).
92. G. E. Riley, C. F. H. Tipper, and R. J. Puddephatt,!. Organomet. Chem. 208, 429 (1981).
93. T. M. McCarthy, R. G. Nuzzo, and G. M. Whitesides, J. Am. Chem. Soc. 103, 3396
(1981).
94. T. J. McCarthy, R. G. Nuzzo, and G. M. Whitesides,!. Am. Chem. Soc. 103, 1676 (1981).
95. R. G. Nuzzo, T. J. McCarthy, and G. M. Whitesides,!. Am. Chem. Soc. 103, 3404 (1981).
96. B. M. Cushman and D. B. Brown, Inorg. Chem. 20, 2490 (1981).
97. R. H. Hill and R. J. Puddephatt, Inorg. Chim. Acta 54, L277 (1981).
98. R. G. Finke, D. A. Schiraldi, and Y. Hirose, J. Am. Chem. Soc. 103,1875 (1981).
1. H. S. Choi and D. A. Sweigart, 1. Organomet. Chem. 228, 249 (1982).
2. G. R. John, L. A. P. Kane-Maguire, and D. A. Sweigart, 1. Organomet. Chem. 120, C47
(1976).
3. C. D. Ritchie and J. Gandler,l. Am. Chem. Soc. 101,7318 (1979), and references therein.
4. R. A. Pickering and R. J. Angelici, 1. Organomet. Chem. 225, 253 (1982).
5. F. B. McCormick and R. J. Angelici, [norg. Chem. 20, 1118 (1981).
6. H. Fischer, J. Miihlemeier, R. Mlirkl, and K. H. Dotz, Chem. Ber. 115,1355 (1982).
7. N. M. Kostic and R. F. Fenske, Organometallics 1,489 (1982).
8. A. Nutton and P. M. Maitlis, 1. Chem. Soc., Dalton Trans., 2335 (1981).
9. O. Eisenstein and R. Hoffmann, 1. Am. Chem. Soc. 103,4308 (1981), and references
therein.
10. T. C. T. Chang, B. M. Foxman, M. Rosenblum, and C. Stockman, 1. Am. Chem. Soc.
103,7361 (1981).
1l. T. C. T. Chang, M. Rosenblum, and S. B. Samuels,l. Am. Chem. Soc. 102, 5930 (1980).
12. M. Green, J. K. K. Sarhan, and I. M. AI-Najjar,!. Chem. Soc., Dalton Trans., 1565 (1981).
13. D. L. Reger, P. J. McElligott, N. G. Charles, E. A. H. Griffith, and E. L. Amma,
Organometallics 1,443 (1982).
14. J. R. Briggs, C. Crocker, W. S. McDonald, and B. L. Shaw, 1. Chem. Soc., Dalton Trans.,
575 (1981).
15. M. Stephenson and R. J. Mawby, 1. Chem. Soc., Dalton Trans., 2112 (1981).
16. B. Akermark and A. Jutland, 1. Organomet. Chem. 217, C41 (1981), and references
therein.
17. H. S. Choi and D. A. Sweigart, Organometallics 1,60 (1982).
18. T. I. Odiaka and L. A. P. Kane-Maguire, 1. Chem. Soc., Dalton Trans., 1162 (1981).
19. L. A. P. Kane-Maguire, T. I. Odiaka, and P. A. Williams, 1. Chem. Soc., Dalton Trans.,
200 (1981).
20. L. A. P. Kane-Maguire, T. I. Odiaka, S. Turgoose, and P. A. Williams, 1. Chem. Soc.,
21. 1. G. Atton and L. A. P. Kane-Maguire, J. Organomet. Chem. 226, C43 (1982).
22. D. A. Brown, W. K. Glass, and F. M. Hussein, J. Organomet. Chem. 218, C15 (1981).
23. G. R. John and L. A. P. Kane-Maguire, 1. Chem. Soc., Dalton Trans., 873 (1979).
24. G. R. John and L. A. P. Kane-Maguire, [norg. Chim. Acta. 48,179 (1981).
25. A. J. Birch, D. Bogsanyi, and L. F. Kelly, 1. Organomet. Chem. 214, C39 (1981).
26. A.l. Birch, Ann. N. Y. Acad. Sci. 333,107 (1980).
27. A. J. Pearson, T. R. Perrior, and D. C. Rees, l. Organomet. Chem. 226, C39 (1982).
28. A. J. Birch and G. R. Stephenson, 1. Organomet. Chem. 218, 91 (1981).
29. D. W. Clack, M. Monshi, and L. A. P. Kane-Maguire, 1. Organomet. Chem. 107, C40
(1976).
30. R. S. Bayoud, E. R. Biehl, and P. C. Reeves, 1. Organomet. Chem. 174,297 (1979).
3l. A. J. Birch, W. D. Raverty, and G. R. Stephenson, 1. Organic Chem. 46, 5166 (1981).
32. G. R. Stephenson, Aust. 1. Chem. 34, 2339 (1981).
33. J. G. Atton, L. A. P. Kane-Maguire, P. A. Williams, and G. R. Stephenson, 1. Organomet.
Chem. 232, C5 (1982).
34. D. J. Evans, L. A. P. Kane-Maguire, and S. B. Wild, 1. Organomet. Chem. 232, C9 (1982).
35. A. C. Knipe, S. J. McGuinness, and W. E. Watts, 1. Chem. Soc., Perkin Trans. 2, 193
(1981).
36. V. V. Litvak, L. S. Filatova, G. A. Selivanova, and V. D. Shteingarts, Zh. Org. Khim.
16,342 (1980) [Chem. Abst. 93, n08C (1980)].
412 References
37. V. V. Litvak, L. S. Filatova, N. U. Khalikova, and V. D. Shteingarts, Zh. Org. Khirn.
16,336 (1980) [Chern. Abst. 93, 7207b (1980)].
38. V. V. Litvak, P. P. Kun, and V. D. Shteingarts, Zh. Org. Khirn. 16, 1009 (1980) [Chern.
Abst. 93, 186508v (1980)).
39. D. J. Evans, L. A. P. Kane-Maguire, and D. A. Sweigart, J. Organornet. Chern. 215,
C27 (1981).
40. J. C. Boutonnet, L. Mordenti, E. Rose, O. Le Martret, and G. Precigoux, J. Organornet.
Chern. 221,147 (1981).
41. J. C. Boutonnet and E. Rose, J. Organornet. Chern. 221, 157 (1981).
42. S. G. Davies, M. L. H. Green, and D. M. P. Mingos, Tetrahedron 34,3047 (1978).
43. A. C. Sievert and E. Muetterties, Inorg. Chern. 20, 2276 (1981).
44. R. N. Hazaldine, R. 1. Lunt, and P. V. Parish, J. Chern. Soc. (A), 3696 (1971).
45. E. Roman, D. Astruc, and H. des Abbayes, J. Organornet. Chern. 219, 211 (1981).
46. C. A. Bunton, N. Carrasco, N. Cully, and W. E. Watts, J. Chern. Soc., Perkin Trans. 2,
1859 (1980).
47. C. A. Bunton, N. Carrasco, F. Davoudzadeh, and W. E. Watts, J. Chern. Soc., Perkin
Trans. 2, 924 (1981).
48. P. C. Reeves, 1. Organornet. Chern. 215, 215 (1981).
49. A. Ceccon, A. Gambaro, G. Agostini, and A. Venzo,l. Organornet. Chern. 217, 79 (1981).
50. H. Brunner and H. Koch, Chern. Ber. 115, 65 (1982).
51. E. Roman, D. Astruc, and A. Darchen, J. Organornet. Chern. 219,221 (1981).
52. A. A. Tsoy, N. K. Baranetskaya, V. N. Setkina, and D. N. Kursanov, J. Organornet.
Chern. 212, 377 (1981).
53. A. Petrou, E. Vrachnou-Astra, J. Konstantatos, N. Katsaros, and D. Katakis, Inorg.
Chern. 20,109] (1981).
54. C. Guimon, G. Pfister-Guillouzo, and E. Rose, J. Organornet. Chern. 224, 125 (1982).
55. S. K. Chopra, M. J. Hynes, and P. McArdle, J. Chern. Soc., Dalton Trans., 586 (1981).
56. S. K. Chopra, G. Moran, and P. McArdle, J. Organornet. Chern. 214, C36 (1981).
1. D. J. Darensbourg, J. Organornet. Chern. 209, C37 (1981).
2. D. J. Darensbourg, R. Kudaroski, and W. Schenk, Inorg. Chern. 21, 2488 (1982).
3. M. Y. Darensbourg and S. Slater, J. Arn. Chern. Soc. 103, 5914 (1981).
4. M. Kotzian, C. G. Kreiter, and S. Ozkar, J. Organornet. Chern. 229, 29 (1982).
5. P. Bischofberger and H.-J. Hanson, Helv. Chirn. Acta 65,721 (1982).
6. C. E. Johnson and W. C. Trogler, Inorg. Chern. 21, 427 (1982).
7. B. J. Brisdon and A. Day, J. Organornet. Chern. 221, 279 (1981).
8. K. von Deuten, D. Rehder, and W. Roose, J. Organornet. Chern. 214, 71 (1981).
9. R. Seeber, G. A. Mazzocchin, E. Roncari, and U. Mazzi, Trans. Met. Chern. 6, 123
(1981).
10. H. Tanaka, K. Isobe, and S. Kawaguchi, Inorg. Chirn. Acta 54, L201 (1981).
11. J. J. MacDougall, J. H. Nelson, and F. Mathey, Inorg. Chern. 21, 2145 (1982).
12. R. Favez and R. Roulet, Inorg. Chern. 20, 1598 (1981).
13. F. Ozawa, T. Ito, Y. Nakamura, and A. Yamamoto, Bull. Chern. Soc. Japan 54, 1868
(1981).
14. W. J. Louw and R. van Eldik, Inorg. Chern. 20, 1939 (1981).
15. G. K. Anderson and R. J. Cross, Inorg. Chern. 20, 4459 (1981).
16. J. H. Nelson and N. W. Alcock, Inorg. Chern. 21, 1196 (1982).
17. H. C. Clark and M. A. Mesubi, 1. Organornet. Chern. 215, 131 (1981).
18. M. K. Cooper and 1. M. Downes, 1. Chern. Soc., Chern. Cornrnun., 381 (1981).
19. J. M. Brown and A. G. Kent, 1. Chern. Soc., Chern. Cornrnun., 723 (1982).
20. N. Serpone and D. G. Bickley, Inorg. Chirn. Acta 57,211 (1982).
21. B. P. Sullivan and T. J. Meyer, Inorg. Chern. 21, 1037 (1982).
22. B. Sarry and R. Schaffernicht, Z. Naturforsch. 36b, 1238 (1981).
23. H. W. Choi and E. L. Muetterties, 1. Arn. Chern. Soc. 104, 153 (1982).
24. D. Baudry, M. Ephritikhine, and H. Felkin, 1. Organornet. Chern. 224, 363 (1982).
25. M. R. Duttera, P. J. Fagan, and T. J. Marks, J. Arn. Chern. Soc. 104, 865 (1982).
26. M. Brookhart, J. R. Tucker, T. C. Flood, and J. Jensen, 1. Arn. Chern. Soc. 102, 1203
(1980).
27. M. Brookhart, J. R. Tucker, and G. R. Husk, J. Arn. Chern. Soc. 103,979 (1981).
28. S. E. Kegley, M. Brookhart, and G. R. Husk, Organornetallics 1, 760 (1982).
29. 1. A. Gladysz, W. K. Wong, and W. Tam, 1. Arn. Chern. Soc. 101, 5440 (1979).
30. F. B. McCormick, W. A. Kiel, and J. A. G1adysz, Organornetallics 1,405 (1982).
31. B. E. Boland-Lussier, M. R. Churchill, R. P. Hughes, and A. L. Rheingold, Organornetal-
lics 1, 628 (1982).
32. F. J. Manganiello, M. D. Radcliffe, and W. M. Jones, 1. Organornet. Chern. 228, 273
(1982).
33. D. Spangler, J. J. Wendlolski, M. Dupuis, M. M. L. Chen, and H. F. Schaefer III, 1.
Arn. Chern. Soc. 103, 3985 (1981).
34. P. J. Hay, J. Arn. Chern. Soc. 103, 1390 (1981).
35. F. R. Hartley, J. Organornet. Chern. 216, 277 (1981).
36. C. G. Kreiter, K. Nist, and H. G. Alt, Chern. Ber. 114,1845 (1981).
37. R. B. A. Pardy, J. Organornet. Chern. 216, C29 (1981).
38. R. S. Herrick and J. L. Templeton, Organornetallics 1, 842 (1982).
39. R. Benn, A. Rufinska, and G. Schroth,l. Organornet. Chern. 217, 91 (1981).
40. A. M. Rosan, J. Chern. Soc., Chern. Cornrnun., 311 (1981).
41. D. H. Gibson, W.-L. Hsu, A. L. Steinmetz, and B. V. Johnson, J. Organornet. Chern.
208,89 (1981).
42. J. W. Faller, Y. Shvo, K. Chao, and H. H. Murray,]. Organornet. Chern. 226, 251 (1982).
43. T. A. Albright, Acc. Chern. Res. 15, 149 (1982).
44. W. D. Luke and A. Streitwieser, Jr., J. Arn. Chern. Soc. 103, 3241 (1981).
45. H. Werner and W. Hofmann, Chern. BeT. 114, 2681 (1981).
46. R. Werner and H. Werner, J. Organornet. Chern. 210, Cll (1981).
47. J. Howard, K. Robson, and T. C. Waddington, J. Chern. Soc., Dalton Trans., 967, 977
(1982).
48. C. Mealli, S. Midollini, J. Moneti, L. Sacconi, J. Silverstre, and T. A. Albright, J. Arn.
Chern. Soc. 104, 95 (1982).
49. J. Blenkers, H. J. De LiefdeMeijer, and J. H. Teuben, J. Organomet. Chem. 218, 383
(1981).
50. M. Rosenblum and P. Waterman, J. Organornet. Chern. 206,197 (1981).
51. L. S. Hegedus, B. Alkermark, D. J. Olsen, O. P. Anderson, and K. Zetterberg, J. Arn.
Chern. Soc. 104, 697 (1982).
52. R. Benn and G. Schroth, 1. Organomet. Chem. 228, 71 (1982), W. Gausing and G.
Wilke, Angew. Chern. Int. Ed. Eng. 20,186 (1981).
53. H. Yasuda, Y. Kajihara, K. Mashima, K. Nagasuna, K. Lee, and A. Nakamura,
Organometallics 1,388 (1982).
54. M. F. Lappert, C. L. Raston, B. W. Skelton, and A. H. White, J. Chem. Soc., Chern.
Commun., 485 (1981).
414 References
55. B. D. Fabian and J. A. Labinger, J. Organornet. Chern. 204, 387 (1981).
56. D. M. Heinekey and W. A. G. Graham, J. Arn. Chern. Soc. 104,915 (1982).
57. R. R. Burch, E. L. Muetterties, and V. W. Day, Organornetallics 1, 188 (1982).
58. F. van Bolhuis, A. H. Klazinga, and J. H. Teuben, J. Organornet. Chern. 206,185 (1981).
59. K. J. Karel, T. A. Albright, and M. Brookhart, Organornetallics 1,419 (1982).
60. A. Ceccon, A. Gambaro, G. Agostini, and A. Venzo, J. Organornet. Chern. 217, 79
(1981).
61. C. A. Ghilardi, P. Innocenti, S. Midollini, and A. Orlandini, J. Organornet. Chern. 231,
C78 (1982).
62. T. J. Mazanec, J. B. Letts, and D. W. Meek, J. Chern. Soc., Chern. Cornrnun., 356 (1982).
63. J. P. Fackler, Jr., L. D. Thompson, I. J. B. Lin, T. A. Stephenson, R. O. Gould, J. M.
C. Alison, and A. J. F. Fraser, Inorg. Chern. 21, 2397 (1982).
64. P. G. Pringle and B. L. Shaw, J. Chern. Soc., Chern. Cornrnun., 581 (1982).
65. c. J. Creswell, M. A. M. Queir6s, and S. D. Robinson, Inorg. Chirn. Acta 60, 157 (1982).
66. E. W. Abel, S. K. Bhargava, P. K. Mittal, K. G. Orrell, and V. Sik, J. Chern. Soc.,
Chern. Cornrnun., 535 (1982).
67. H. van der Poe I and G. van Koten, J. Organornet. Chern. 217,129 (1981).
68. R. B. A. Pardy, M. J. Taylor, E. C. Constable, F. D. Mersh, and J. K. M. Sanders, J.
Organornet. Chern. 231, C5 (1982).
69. W. Lamanna and M. Brookhart, J. Arn. Chern. Soc. 103, 989 (1981).
70. P. Bladon, G. A. M. Munro, P. L. Pauson, and C. A. L. Mahaffy, J. Organornet. Chern.
221,79 (1981).
71. M. Brookhart, W. Lamanna, and M. B. Humphrey, J. Arn. Chern. Soc. 104,2117 (1982).
72. M. A. Bennett, I. J. McMahon, and T. W. Turney, Angew. Chern. Int. Ed. Eng. 21,
379 (1982); Angew. Chern. Suppl., 853 (1982).
73. O. W. Howarth, C. H. McAteer, P. Moore, and G. E. Morris, J. Chern. Soc., Chern.
Cornrnun., 506 (1981).
74. F. D. Fellmann, R. R. Schrock, and D. D. Traficante, Organornetallics 1,481 (1982).
75. M. R. Churchill, H. J. Wasserman, H. W. Turner, and R. R. Schrock, J. Arn. Chern.
Soc. 104, 1710 (1982).
76. S. S. M. Ling and R. J. Puddephatt, J. Chern. Soc., Chern. Cornrnun., 412 (1982).
77. K. Brown and P. A. Chaloner, J. Organornet. Chern. 217, C25 (1981).
78. K. Hiraki, Y. Fuchita, and K. Takechi, Inorg. Chern. 20, 4316 (1981).
79. F. G. Riddell, R. D. Gillard, and F. L. Wimmer, J. Chern. Soc., Chern. Cornrnun., 332
(1982).
80. M. K. Deh, R. D. W. Kemmitt, P. McKenna, D. R. Russell, and L. J. S. Sherry, J.
Chern. Soc., Chern. Cornrnun., 505 (1982).
81. E. W. Abel, M. Booth, C. A. Brown, K. G. Orrell, and R. L. Woodford, J. Organornet.
Chern. 214, 93 (1981).
82. E. W. Abel, M. Booth, and K. G. Orrell, J. Organornet. Chern. 208, 213 (1981).
83. E. W. Abel, M. M. Bhatti, K. G. Orrell, and V. Sik, J. Organornet. Chern. 208, 195
(1981).
84. E. W. Abel, A. R. Khan, K. Kite, K. G. Orrell, and V. Sik, J. Organornet. Chern. 225,
357 (1982).
85. E. W. Abel, S. K. Bhargava, K. Kite, K. G. Orrell, V. Sik, and B. L. Williams, J. Chern.
86. E. W. Abel, S. K. Bhargava, K. Kite, K. G. Orrell, V. Sik, and B. L. Williams, Polyhedron
1,289 (1982).
87. S. A. R. Knox, R. F. D. Stansfield, F. G. A. Stone, M. J. Winter, and P. Woodward,
J. Chern. Soc., Dalton Trans., 167 (1982).
415
88. J. A. Marsella and K. G. Caulton, Organornetallics 1, 274 (1982).
89. D. M. Adams, P. D. Hatton, A. C. Shaw, and T.-K. Tan, 1. Chern. Soc., Chern. Cornrnun.,
226 (1981).
90. 1. C. Jeffery, H. Razay, and F. G. A. Stone, 1. Chern. Soc., Chern. Cornrnun., 243 (1981).
91. W. I. Bailey, A. Bino, F. A. Cotton, B. W. S. Kolthammer, P. Lahuerta, P. Puebla,
and R. Uscn, Inorg. Chern. 21, 289 (1982).
92. L. H. Staal, J. Keijsper, L. H. Polm, and K. Vrieze, 1. Organornet. Chern. 204, 101 (1981).
93. M. A. Green, J. C. Huffman, and K. G. Caulton, 1. Arn. Chern. Soc. 104,2319 (1982).
94. R. B. Wilson, Jr., A. P. Sattel berger, and J. C. Huffman 1. Arn. Chern. Soc. 104, 858
(1982).
95. R. S. Threlkel and J. E. Bercaw, 1. Arn. Chern. Soc. 103, 2650 (1981).
96. G. M. Dawkins, M. Green, A. G. Orpen, and F. G. A. Stone, 1. Chern. Soc., Chern.
Cornrnun., 41 (1981).
97. C. P. Casey, P. J. Fagan, and W. H. Miles, 1. Arn. Chern. Soc. 104, 1134 (1982).
98. A. F. Dyke, S. A. R. Knox, K. A. Mead, and P. Woodward, 1. Chern. Soc., Chern.
Cornrnun., 861 (1981).
99. A. Salzer, T. Egolf, and W. von Philipsborn, Helv. Chirn. Acta 65, 1145 (1982).
100. E. W. Abel, M. Booth, K. G. Orrell, G. M. Pring, and T. S. Cameron, 1. Chern. Soc.,
101. R. J. Puddephatt, M. A. Thomson, L. Manojlovic-Muir, K. W. Muir, A. A. Frew, and
M. P. Brown, 1. Chern. Soc., Chern. Cornrnun., 805 (1981).
102. G. Jaouen, A. Marinetti, J.-Y. Saillard, B. G. Sayer, and M. J. McGlinchey, Organornetai-
lics 1, 225 (1982).
103. R. E. Benfield and B. F. G. Johnson, Trans. Met. Chern. 6,131 (1981).
104. H. Dorn, B. E. Hanson, and E. Motell, Inorg. Chirn. Acta 54, L71 (1981).
105. A. A. Koridze, o. A. Kizas, N. N. Astakhova, P. V. Petrovskii, and Yu. K. Grishin, 1.
Chern. Soc., Chern. Cornrnun., 853 (1981).
106. S. Aime and D. Osella, 1. Organornet. Chern. 214, C27 (1981).
107. C. Barner-Thorsen, K. I. Hardcastle, E. Rosenberg, J. Siegel, A. M. Manotti Lanfredi,
A. Tiripicchio, and M. Tiripicchio Camellini, Inorg. Chern. 20, 4306 (1981).
108. N. D. Feasey, S. A. R. Knox, and A. G. Orpen, 1. Chern. Soc., Chern. Cornrnun., 75
(1982).
109. c. C. Nagel, J. C. Bricker, D. G. Alway, and S. G. Shove, 1. Organornet. Chern. 219,
C9 (1981).
110. B. T. Heaton, L. Strona, J. Jonas, T. Eguchi, and G. A. Hoffman, 1. Chern. Soc., Dalton
Trans., 1159 (1982).
111. W. Abboud, Y. Ben Taarit, R. Mutin, and J.-M. Basset, 1. Organornet. Chern. 220, C15
(1981).
112. B. T. Heaton, L. Strona, and S. Martinengo, 1. Organornet. Chern. 215, 415 (1981).
113. W. A. Herrmann, H. Biersack, M. L. Ziegler, K. Weiderhammer, R. Siegel, and D.
Rehder, 1. Arn. Chern. Soc. 103, 1692 (1981).
114. E. C. Constable, B. F. G. Johnson, J. Lewis, G. N. Pain, and M. J. Taylor, 1. Chern.
Soc., Chern. Cornrnun., 754 (1982).
115. S. Aime, D. Osella, L. Milone, and E. Rosenberg, 1. Organornet. Chern. 213, 207 (1981).
116. M. Green, J. A. K. Howard, R. M. Mills, G. N. Pain, F. G. A. Stone, and P. Woodward,
1. Chern. Soc., Chern. Cornrnun., 869 (1981).
117. M. Green, D. R. Hankey, M. Murray, A. G. Orpen, and F. G. A. Stone, 1. Chern. Soc.,
118. M. R. Churchill, C. Bueno, S. Kennedy, J. C. Bricker, J. S. Plotkin, and S. G. Shove,
Inorg. Chern. 21,627 (1982).
416 References
119. K. Henrick, M. McPartlin, A. J. Deeming, S. Hasso, and P. Manning, l. Chern. Soc.,
120. J. Evans and G. S. McNulty, l. Chern. Soc., Dalton Trans., 2017 (1981).
121. R. D. Adams, D. A. Katahira, and L.-W. Yang, Organornetallics 1,235 (1982).
122. A. J. Deeming, I. P. Rothwell, M. B. Hursthouse, and J. D. J. Backer-Dirks, l. Chern.
123. L. Busetto, M. Green, J. A. K. Howard, B. Hessner, J. C. Jeffery, R. M. Mills, F. G.
A. Stone, and P. Woodward, l. Chern. Soc., Chern. Cornrnun., 1101 (1981).
124. M. R. Churchill, C. Bueno, and H. J. Wasserman, Inorg. Chern. 21, 640 (1982).
125. S. Aime, L. Milone, D. Osella, A. Tiripicchio, and A. M. Manotti Lanfredi, Inorg.
Chern. 21, 501 (1982).
126. G. Jaouen, A. Marinetti, B. Mentzen, R. Matin, J.- Y. Saillard, B. G. Sayer, and M. J.
McGlinchey, Organornetallics 1,753 (1982).
127. R. T. Edidin, J. R. Norton, and K. Mislow, Organornetallics 1,561 (1982).
128. S. Aime, R. Gobetto, D. Osella, L. Milone, and E. Rosenberg, Organornetallics 1,640
(1982).
129. S. Aime, G. Jannon, D. Osella, and A. J. Deeming, l. Organornet. Chern. 214, C15
(1981).
130. J. A. S. Howell and P. Mathur, l. Chern. Soc., Chern. Cornrnun., 263 (1981); l. Chern.
Soc., Dalton Trans. 43 (1982).
1. K. Tatsumi and M. Tsutsui, l. Mol. Catal. 13, 117 (1981).
2. E. Cesarotti, R. Ugo, and L. Kaplan, Coord. Chern. Rev. 43, 275 (1982).
3. R. M. Laine, l. Mol. Catal. 14, 137 (1982).
4. P. Heimbach, H. Schenkluhn, and K. Wisseroth, Pure Appl. Chern. 53, 2419 (1981).
5. H. Alper, Adv. Organornet. Chern. 19, 183 (1981).
6. B. Bosnich and M. D. Fryzuk, Top Stereochern. 12, 119 (1981); R. E. Merrill, Cherntech
11, 118 (1981); U. Matteoli, P. Frediani, M. Bianchi, C. Botteghi, and S. Gladiali, l.
Mol. Catal. 12, 265 (1981); H. Wynberg, Reel.: l.R. Neth. Chern. Soc. 100,393 (1981).
7. M. Gratzel, Acc. Chern. Res. 14, 376 (1981); P. K. Eidem, A. W. Maverick, and H.
B. Gray, Inorg. Chern. Acta 50,59 (1981).
8. J. F. McGarrity, J. Prodolliet, and T. Smyth, Org. Magn. Reson. 17, 59 (1981).
9. J. D. Fellmann, R. R. Schrock, and D. D. Traficante, Organornetallics (Washington
D.C.) 1, 481 (1982).
10. S. S. M. Ling and R. J. Puddephatt, l. Chern. Soc. Chern. Cornrnun., 412 (1982).
11. C. Botteghi, S. Gladiali, V. Bellagamba, R. Ercoli, and A. Gamba, Chirn. Ind. (Milan)
62,604,757 (1980); 63, 29 (1981); T. Yamanaka, Kagaku Kogyo 32, 116,212 (1981).
12. D. Forster, A. Hershman, and D. E. Morris, Catal. Rev.-Sci. Eng. 23, 89 (1981).
13. P. C. Ford, ed., Catalytic Activation of Carbon Monoxide, (The American Chemical
Society, Washington, D.C., 1981).
14. (a) M. J. Mirbach, N. Topalsavoglu, T. N. Phu, M. F. Mirbach, and A. Saus, l. Am.
Chern. Soc. 103, 7590 (1981); (b) l. Am. Chern. Soc. 103, 7594 (1981); (c) Angew.
Chern. Int. Ed. Engl. 20, 381 (1981).
15. G. Kohl, M. Kinne, L. Schroeder, H. Fischer, N. S. Imyanitov, B. E. Kuvaev, and M.
P. Vysotskii, Chern. Tech. (Leipzig) 33, 629 (1981).
16. M. Royo, F. Melo, A. Manrique, and L. Oro, Transition Met. Chern. 7, 44 (1982).
17. (a) G. Gregorio, G. Montrasi, M. Tampieri, P. Cavalieri d'Oro, G. Pagani, and A.
Andreetta, Chirn. Ind. (Milan) 62, 389 (1980); (b) P. Cavalieri d'Oro, L. Raimondi,
G. Pagani, G. Montrasi, G. Gregorio, and A. Andreetta, Chern. Ind. (Milan) 62, 572
(1980); (c) G. Montrasi, G. Pagani, G. Gregorio, P. Cavalieri d'Oro, and A. Andreetta,
Chern. Ind. (Milan) 62, 737 (1980).
18. T. Hayashi, M. Tanaka, and I. Ogata, l. Mol. Catal. 13, 323 (1981).
19. (a) c. Vaccher, A. Mortreux, and F. Petit, l. Mol. Catal. 12, 329 (1981); (b) J. D.
Unruh and J. R. Christenson, l. Mol. Catal. 14, 19 (1981); (c) S. Franks and F. R.
Hartley, l. Mol. Catal. 12, 121 (1981).
20. T. Fuchikami and I. Ojima, l. Arn. Chern. Soc. 104, 3527 (1982).
21. (a) O. R. Hughes and D. A. Young, l. Arn. Chern. Soc. 103,6636 (1981); (b) O. R.
Hughes and J. D. Unruh, l. Mol. Catal. 12,71 (1981).
22. H. C. Clark and J. A. Davies, l. Organornet. Chern. 213, 503 (1981).
23. T. Hayashi, Y. Kawabata, T. Isoyama, and I. Ogata, Bull. Chern. Soc. lpn. 54, 3438
(1981).
24. S. C. Tang and L. Kim, l. Mol. Catal. 14, 231 (1982).
25. R. Bardi, A. M. Piazzesi, G. Cavinato, P. Cavoli, and L. Toniolo, l. Organornet. Chern.
224,407 (1982).
26. G. K. Anderson, H. C. Clark, and J. A. Davies, Organornetallics (Washington D.C.)
1,64 (1982).
27. P. Haelg, G. Consiglio, and P. Pino, Helv. Chirn. Acta 64, 1865 (1981).
28. (a) C. U. Pittman, Jr., Y. Kawabata, and L. I. Flowers, l. Chern. Soc. Chern. Cornrnun.,
473 (1982); (b) I. Schwager and J. K. Knifton; l. Catal. 45, 256 (1976).
29. c. F. Hobbs and W. S. Knowles, l. Org. Chern. 46,4422 (1981).
30. G. Cavinato and L. Toniolo, l. Mol. Catal. 10, 161 (1981).
31. (a) A. Matsuda, Tokyo Kogyo Shikensho Hokoku 75, 419 (1980); (b) Tokyo Kogyo
Shikensho Hokoku 75,445 (1980).
32. D. H. Doughty, M. P. Anderson, A. L. Casalnuovo, M. F. McGuiggan, C. C. Tso, H.
H. Wang, and L. H. Pignolet, Adv. Chern. Ser. 196, 65 (1982).
33. A. Masuda, H. Mitani, K. Oku, and Y. Yamazaki, Nippon Kagaku Kaishi, 249 (1982).
34. G. Doyle, 1. Mol. Catal. 13, 237 (1981).
35. Y. Sugi, K. Bando and Y. Takami, Chern. Lett., 63 (1981).
36. T. Kobayashi and M. Tanaka, l. Organornet. Chern. 205, C27 (1981).
37. F. Francalanci and M. Foa, l. Organornet. Chern. 232, 59 (1981).
38. J. F. Knifton, Cherntech 11,609 (1981); l. Chern. Soc., Chern. Cornrnun., 41 (1981);
l. Mol. Catal. 11, 91 (1981).
39. G. Braca, L. Paladini, G. Sbrana, G. Valentini, G. Andrich, and G. Guglielmo, Ind.
Eng. Chern. Prod. Res. Dev. 20, 115 (1981).
40. J. B. Keister and R. Gentile, l. Organornet. Chern. 222,143 (1981).
41. M. Schrod and G. Luft, Ind. Eng. Chern. Prod. Res. Dev. 20, 649 (1981).
42. V. I. Manov-Yuvenskii and B. K. Nefedov, Russ. Chern. Rev. (Engl. Trans.) 50, 470
(1981).
43. J. R. Blackborow, R. J. Daroda, and G. Wilkinson, Coord. Chern. Rev. 43,17 (1982);
W. A. Herrmann, Angew. Chern. Int. Ed. Engl. 21, 117 (1982); M. Hidai, Kagaku
(Kyoto) 37,187 (1982); C. K. Rofer-DePoorter, Chern. Rev. 81, 447 (1981); G. A.
Somorjai, Catal. Rev.-Sci. Eng. 23, 189 (1981); D. L. King, J. A. Cusamano, and R.
L. Garten, Catal. Rev.-Sci. Eng. 23, 233 (1981).
44. J. R. Sweet and W. A. G. Graham, l. Arn. Chern. Soc. 104, 2811 (1982).
45. (a) W. Tam, G. Y. Lin, W. K. Wong, W. A. Kiel, V. K. Wong, and J. A. Gladysz, l.
Arn. Chern. Soc. 104, 141 (1982); (b) B. B. Wayland, B. A. Woods, and R. Pierce, l.
418 References
Arn. Chern. Soc. 104, 302 (1982); (c) c. P. Casey, M. A. Andrews, D. R. McAlister,
W. D. Jones, and S. G. Harsy, 1. Mol. Catal. 13,43 (1981).
46. G. R. Steinmetz and G. L. Geoffroy, 1. Arn. Chern. Soc. 103, 1278 (1981).
47. G. Fachinetti, R. Lazzaroni, and S. Pucci, Angew. Chern. Int. Ed. Engl. 20, 1063
(1981).
48. J. A. Marsella, K. Folting, J. C. Huffman, and K. G. Caulton, 1. Arn. Chern. Soc. 103,
5596 (1981).
50. D. R. Fahey, 1. Arn. Chern. Soc. 103, 136 (1981).
51. (a) Henrici-Olive and S. Olive, Angew. Chern. Int. Ed. Engl. 18, 77 (1979); (b) L. S.
Benner, Y. H. Lai, and K. P. C. Vollhardt,l. Arn. Chern. Soc. 103, 3609 (1981).
52. (a) R. J. Daroda, J. R. Blackborow, and G. Wilkinson, 1. Chern. Soc. Chern. Cornrnun.,
1098 (1980); (b) T. E. Paxson, C. A. Reilly, and D. R. Holecek, 1. Chern. Soc. Chern.
Cornrnun., 618 (1981).
53. (a) M. G. Thomas, B. F. Beier and E. L. Muetterties, 1. Arn. Chern. Soc. 98, 1296
(1976); (b) R. A. Schunn, G. C. Demitras, H. W. Choi, and E. L. Muetterties, Inorg.
Chern. 20, 4023 (1981).
54. P. C. Ford, Acc. Chern. Res. 14, 31 (1981).
55. A. D. King, jun., R. B. King, and D. B. Yang, 1. Arn. Chern. Soc. 103,2699 (1981).
56. S. Attali, R. Mathieu, and G. J. Leigh, 1. Mol. Catal. 14,293 (1982).
57. D. J. Darensbourg, A. Rokicki, and M. Y. Darensbourg, 1. Arn. Chern. Soc. 103, 3223
(1981).
58. A. D. King, jun., R. B. King, and E. L. Sailers, III, 1. Am. Chern. Soc. 103, 1867 (1981).
59. R. G. Pearson and H. Mauermann, 1. Arn. Chern. Soc. 104, 500 (1982).
60. D. C. Gross and P. C. Ford, Inorg. Chern. 21, 1702 (1982).
61. J. C. Bricker, C. C. Nagel, and S. G. Shore, 1. Am. Chern. Soc. 104, 1444 (1982).
62. T. Yoshida, T. Okano, Y. Veda, and S. Otsuka, 1. Arn. Chern. Soc. 103, 3411 (1981).
63. R. A. Sheldon and J. K. Kochi, Metal-Catalyzed Oxidations of Organic Cornpounds
(Academic Press, New York, 1981).
64. H. Mimoun, Pure Appl. Chern. 53, 2389 (1981).
65. J. Sobczak and J. J. Ziolkowski, 1. Mol. Catal. 13, 11 (1981); W. M. H. Sachtler, C.
Backx, and R. A. Van Santen, Ca ta I. Rev.-Sci. Eng. 23, 127 (1981); R. A. Sheldon,
Aspects Homogeneous Catal. 4, 3 (1981).
66. H. J. Ledon, P. Durbut, and F. Varescon, 1. Arn. Chern. Soc. 103, 3601 (1981).
67. O. Bortolini, F. Di Furia, and G. Modena, 1. Mol. Catal. 14, 53 (1982); O. Bortolini,
F. Di Furia, G. Modena, C. Scardellato, and P. Scrimin, 1. Mol. Catal. 11, 107 (1981).
68. o. Bortolini, C. Campello, F. Di Furia, and G. Modena, 1. Mol. Catal. 14, 63 (1982).
69. F. Di Furia, G. Modena, R. Curci, S. J. Bachofer, J. O. Edwards, and M. Pomerantz,
1. Mol. Catal. 14, 219 (1982).
70. V. S. Martin, S. S. Woodward, T. Katsuki, Y. Yamada, M. Ikeda, and K. B. Sharpless,
1. Am. Chern. Soc. 103, 6237 (1981).
71. G. V. Badasyan, S. M. Gabrielyan, G. L. Kamalov, and Yu. A. Treger, Arm Khirn.
Zh., 33, 794 (1980).
72. C. A. McAuliffe, 1. Organornet. Chern. 228, 255 (1982); M. L. H. Green, 1. Organomet.
Chern. 228, 263 (1982).
73. B. A. Moyer, B. K. Snipe, and T. J. Meyer, Inorg. Chern. 20, 1475 (1981).
74. F. M. Agaev, F. Z. Abdullaev, A. G. Gashimov, and S. D. Mekhtiev, Dokl. Akad.
Nauk Az. SSR 36, 40 (1980); Yu. V. Geletii and I. V. Zakharov, Kinet. Katal. 22,
261 (1981); F. V. Nazimok, V. N. Kulakov, and T. A. Simonova, Azerb. Khirn Zh.,
101 (1981); V. F. Gaevskii and N. P. Evmenenko, Ukr. Khirn Zh (Russ Ed.) 48, 160
(1982).
419
75. (a) I. Apostol, J. Haber, T. Mlodnicka, and J. Poltowicz, J. Mol. Catal. 14, 197 (1982);
(b) J. Vcelak, Collect. Czech. Chern. Cornrnun. 46, 201 (1981).
76. B. S. Tovrog, S. E. Diamond, F. Mares, and A. Szalkiewicz, J. Arn. Chern. Soc. 103,
3522 (1981).
77. M. A. Andrews and K. P. Kelly, J. Arn. Chern. Soc. 103, 2894 (1981).
78. L. Carlton and G. Read, J. Mol. Catal. 10, 133 (1981).
79. M. T. Atlay, M. Preece, G. Strukul, and B. R. James, J. Chern. Soc. Chern. Cornrnun.,
406 (1982).
80. A. V. Devekki, Yu. N. Koshelev, and D. V. Muchenko, Zh. Org. Khirn. 16, 2518
(1980); A. V. Devekki, D. V. Mushenko, and V. S. Fedowv, Zh. Org. Khirn. 17,2519
(1981).
81. J. E. Backvall and R. E. Nordberg, J. Arn. Chern. Soc. 103,4959 (1981).
82. N. Gragor and P. M. Henry, J. Arn. Chern. Soc. 103,681 (1981).
83. R. Hamilton, T. R. B. Mitchell, and J. J. Rooney, J. Chern. Soc., Chern. Cornrnun., 456
(1981).
84. K. Cihova, M. Krusovsky, J. Voitko, and K. I. Matveev, React. Kinet. Catal. Lett. 16,
383 (1981).
85. (a) T. R. Demmin, M. D. Swerdloff, and M. M. Rogic, J. Arn. Chern. Soc. 103, 5795
(1981); (b) G. S. Vigee and E. E. Eduok, Inorg. Nucl. Chern. 43, 2171 (1981).
86. R. F. Jameson and N. J. Blackburn, J. Chern. Soc., Dalton Trans. 9 (1982).
87. K. Kaneda, T. Itoh, N. Kii, K. Jitsukawa, and S. Teranishi, f. Mol. Catal. 15,349 (1982).
88. C. Jallabert, C. Lapinte, and H. Riviere, f. Mol. Catal. 14,75 (1982).
89. T. S. Janik, M. F. Pyszczek, and J. D. Atwood, f. Mol. Catal. 11, 33 (1981).
90. H. Kanai, N. Yamamoto, K. Kishi, K. Mizuno, and K. Tarama, J. Catal. 73, 228 (1982).
91. A. Dedieu, A. Strich, and A. Rossi, Ouanturn Theory Chern. React. 2,193 (1981).
92. J. Halpern, Inorg. Chirn. Acta 50, 11 (1981).
93. M. H. J. M. De Croon and J. W. E. Coenen, f. Mol. Catal. 11, 301 (1981).
94. M. Czakova and M. Capka, J. Mol. Catal. 11, 313 (1981).
95. J. M. Brown, P. A. Chaloner, A. G. Kent, B. A. Murrer, P. N. Nicholson, D. Parker,
and P. J. Sidebottom, f. Organornet. Chern. 216, 263 (1981); G. Descotes, D. Lafont,
D. Sinou, J. M. Brown, P. A. Chaloner, and D. Parker, Nouv. f. Chirn. 5, 167 (1981).
96. W. Abboud, Y. B. Taarit, R. Mutin, and J. M. Basset, f. Organornet. Chern. 220, C15
(1981).
97. J. Niewahner and D. W. Meek, Adv. Chern. Ser. 196, 257 (1982).
98. M. M. Taqui Khan, M. Ahmed, and B. Swamy,Indianf. Chern., Sect. A 20A, 359 (1981).
99. J. E. Hamlin, K. Hirai, V. C. Gibson, and P. M. Maitlis, f. Mol. Catal. 15, 337 (1982).
100. T. Okano, T. Kobayashi, H. Konishi, and J. Kiji, Bull. Chern. Soc. fpn. 54, 3799 (1981).
101. B. Longato and S. Bresadola, Inorg. Chern. 21, 168 (1982).
102. L. P. Shuikhina, A. I. EI'natanova, L. S. Kovaleva, O. P. Parenago, and V. M. Froio v,
Kinet. Katal. 22, 177 (1981).
103. A. S. Berenblyum, S. L. Mund, L. G. Danilova, and I. I. Moiseev, !zv. Akad. Nauk
SSSR, Ser. Khirn., 905 (1981).
104. G. Folcher, J. F. Le and H. Marquet-Ellis, J. Chern. Soc. Chern. Cornrnun.,
323 (1982).
105. (a) E. L. Muetterties, Inorg. Chirn. Acta 50, 1 (1981); (b) J. R. BIeeke and E. L.
Muetterties, f. Arn. Chern. Soc. 103, 556 (1981).
106. T. T. Derencsenyi, Inorg. Chern. 20,665 (1981).
107. S. Tyrlik, M. Kwiecinski, and L. Kawczynski, Collect. Czech. Chern. Cornrnun. 46, 1947
(1981).
108. K. Kaneda, M. Hiraki, T. Imanaka, and S. Teranishi, f. Mol. Catal. 12, 385 (1981).
420 References
109. B. R. Cho and R. M. Laine, l. Mol. Catal. IS, 383 (1982).
110. S. Bhaduri and K. R. Sharma, l. Chern. Soc., Dalton Trans., 727 (1982).
111. (a) H. Fujitsu, E. Matsumura, K. Takeshita, and I. Mochida, l. Chern. Soc. Perkin Trans.
1, 2650 (1981); (b) H. Fujitsu, S. Shirahama, E. Matsumura, K. Takeshita, and I.
Mochida, l. Org. Chern. 46, 2287 (1981).
112. M. M. Kucharska and S. Tyrlik, React. Kinet. Catal. Lett. IS, 137 (1980).
113. R. A. Sanchez-Delgado, A. Andriollo, O. L. De Ochoa, T. Suarez, and N. Valencia,
l. Organornet. Chern. 209, 77 (1981).
114. (a) M. I. Kalinkin, S. M. Markosyan, D. N. Kursanov, and Z. N. Parnes, Izv. Akad.
Nauk SSSR Ser Khirn., 675 (1981); (b) S. M. Markosyan, M. I. Kalinkin, Z. N. Parnes,
and D. N. Kursanov, Dokl. Akad. Nauk SSSR 255,599 (1980).
115. V. Caplar, G. Comisso, and V. Sunjic, Synthesis, 85 (1981).
116. J. M. Brown, P. A. Chaloner, and D. Parker, Adv. Chern. Ser. 196, 355 (1982).
117. B. Bosnich and N. K. Roberts, Adv. Chern. Ser. 196, 337 (1982).
118. E. Cesarotti, R. Ugo, and R. Vitiello, l. Mol. Catal. 12,63 (1981).
119. S. Takeuchi and Y. Ohgo, Bull. Chern. Soc. lpn. 54, 2136 (1981).
120. B. R. Stults, R. M. Friedman, K. Koenig, and W. Knowles, l. Arn. Chern. Soc. 103,
3235 (1981).
121. K. Achiwa, P. A. Chaloner, and D. Parker, l. Organornet. Chern. 218, 249 (1981).
122. R. G. Ball, B. R. James, D. Mahajan, and J. Trotter, Inorg. Chern. 20, 254 (1981).
123. (a) D. Sinou, D. Lafont, G. Descotes, and A. G. Kent, l. Organornet. Chern. 217, 119
(1981); (b) D. Sinou, Tetrahedron Lett. 22, 2987 (1981).
124. P. S. Chua, N. K. Roberts, B. Bosnich, S. J. Okrasinski, and J. Halpern, l. Chern. Soc.,
125. P. A. MacNeil, N. K. Roberts, and B. Bosnich, l. Arn. Chern. Soc. 103, 2273 (1981).
126. J. W. Scott, D. D. Keith, G. Nix, jun., D. R. Parish, S. Remington, G. P. Roth, J. M.
Townsend, D. Valentine, Jr., and R. Young, 1. Org. Chern. 46, 5086 (1981).
127. G. Mestroni, A. Camus, and G. Zassinovich, Aspects Hornogeneous Catal. 4, 71 (1981).
128. M. A. Green, J. C. Huffman, K. G. Caulton, W. K. Rybak, and J. J. Ziolkowski, l.
Organornet. Chern. 218, C39 (1981).
129. V. S. Lenenko, A. G. Knizhnik, E. I. Mysov, V. B. Shur, and M. E. Vol'pin, Dokl.
Akad. Nauk SSSR 255, 1131 (1980).
130. W. Strohmeier and B. Graser, Z. Phys. Chern. (Wiesbaden) 12,121 (1980).
131. G. Speier and L. Marko, l. Organornet. Chern. 210, 253 (1981).
132. Y. Blum, D. Reshef, and Y. Shvo, Tetrahedron Lett. 22, 1541 (1981).
133. D. Beaupere, L. Nadjo, R. Uzan, and P. Bauer, l. Mol. Catal. 14, 129 (1982).
134. F. Martinelli, G. Mestroni, A. Camus, and G. Zassinovich, l. Organornet. Chern. 220,
383 (1981).
135. G. Zassinovich, C. D. Bianco, and G. Mestroni, l. Organornet. Chern. 222, 323 (1981).
136. J. Kaspar, R. Spogliarich, and M. Graziani, l. Organornet. Chern. 231, 71 (1982).
137. J. Muzart and J. P. Pete, l. Mol. Catal. IS, 373 (1982).
138. A. S. Berenblyum, A. G. Knizhnik, S. L. Mund, and I. I. Moiseev, Izv. Akad. Nauk
SSSR, Ser. Khirn., 2700 (1980).
139. D. B. Chase and F. J. Weigert, l. Arn. Chern. Soc. 103, 977 (1981).
140. F. Petit, C. Arzouyan, G. Peiffer, and E. Gaydou, l. Organornet. Chern. 208, 261 (1981).
141. T. W. Lai, Inorg. Chern. 20,4036 (1981).
142. M. Cihova, J. Vojtko, M. Hrusovsky, and M. Kiss, Chern. Prurn. 30, 589 (1980).
143. M. Sakai, M. Takahashi, Y. Sakakibara, and N. Uchino, Nippon Kagaku Kaishi, 1283
(1981).
144. G. Giacomelli, L. Bertero, L. Lardicci, and R. Menicagli, l. Org. Chern. 46, 3707 (1981).
421
145. K. Tani, T. Yamagata, S. Otsuka, S. Akutagawa, H. Kumobayashi, T. Taketomi, H.
Takaya, A. Miyashita, and R. Noyori, I. Chern. Soc. Chern. Cornrnun., 600 (1982).
146. R. B. Taylor and P. W. Jennings, Inorg. Chern. 20, 3997 (1981).
147. M. Suzuki, Y. Oda, and R. Noyori, Tetrahedron Lett. 22, 4413 (1981).
148. T. Izumi and H. Alper, Organornetallics (Washington D.C.) 1, 322 (1982).
149. B. M. Trost and T. A. Runge, I. Arn. Chern. Soc. 103,2485, 7550, 7559 (1981).
150. A. Miyashita, M. Takahashi, and H. Takaya, I. Arn. Chern. Soc. 103,6257 (1981).
151. R. L. Banks, Catalysis 4, 100 (1981).
152. Fourth International Symposium on Metathesis, Belfast, I. Mol. Catal. IS, 1-270 (1982).
153. (a) J. Kress, M. Wesolek, J. P. Le Ny, and J. A. Osborn, I. Chern. Soc. Chern. Cornrnun.,
1039 (1981); (b) J. Kress, M. Wesolek, and J. A. Osborn, I. Chern. Soc. Chern. Cornrnun.,
514 (1982).
154. B. A. Dolgoplosk, I. Mol. Catal. IS, 193 (1982).
155. L. Bencze and J. Engelhardt, I. Mol. Catal. IS, 123 (1982).
156. O. Eisenstein, R. Hoffmann, and A. R. Rossi, I. Arn. Chern. Soc. 103, 5582 (1981);
R. J. McKinney, T. H. Tulip, D. L. Thorn, T. S. Coolbaugh, and F. N. Tebbe, I. Arn.
Chern. Soc. 103, 5584 (1981); J. B. Lee, G. J. Gajda, W. P. Schaefer, T. R. Howard,
T. Ikariya, D. A. Straus, and R. H. Grubbs, I. Arn. Chern. Soc. 103,7358 (1981).
157. S. S. Moore, R. DiCosimo, A. F. Sowinski, and G. M. Whitesides, I. Arn. Chern. Soc.
103,949 (1981).
158. H. T. Dodd and K. J. Rutt, I. Mol. Catal. IS, 103 (1982).
159. A. K. Rappe and W. A. Goddard III, I. Arn. Chern. Soc. 104,448 (1982).
160. K. J. Ivin, B. S. R. Reddy, and J. J. Rooney, I. Chern. Soc. Chern. Cornrnun., 1062
(1981).
161. G. J. Leigh, M. T. Rahman, and D. R. Walton, I. Chern. Soc. Chern. Cornrnun., 541
(1982).
162. (a) J. H. Wengrovius, J. Sancho, and R. R. Schrock, I. Arn. Chern. Soc. 103, 3932
(1981); (b) J. Sancho and R. R. Schrock, I. Mol. Catal. IS, 75 (1982).
163. A. Bencheick, M. Petit, A. Mortreux, and F. Petit, I. Mol. Catal. IS, 93 (1982).
164. R. H. A. Bosma, X. D. Xu, and J. C. Mol, I. Mol. Catal. IS, 187 (1982); H. H. Thoi,
K. J. Ivin, and J. J. Rooney, I. Mol. Catal. IS, 245 (1982).
165. C. Larroche, J. P. Laval, A. Lattes, M. Leconte, F. Ouignard, and J. M. Basset, I. Org.
Chern. 47, 2019 (1982); N. Taghizadeh, F. Ouignard, M. Leconte, J. M. Basset, C.
Larroche, J. P. Laval, and A. Lattes, I. Mol. Catal. IS, 219 (1982).
166. A. Uchida, M. Hinenoya, and T. Yamamoto, I. Chern. Soc., Dalton Trans., 1089 (1981).
167. K. C. Ott, J. B. Lee, and R. H. Grubbs, I. Arn. Chern. Soc. 104, 2942 (1982).
168. V. A. Zakharov, G. D. Bukatov, and Yu.1. Ermakov, Russ. Chern. Rev. (Engl. Transl.)
49,1097 (1981); G. Henrici-Olive and S. Olive, Cherntech., 746 (1981).
169. P. L. Watson, I. Arn. Chern. Soc. 104, 337 (1982).
170. (a) J. D. Fellmann, R. R. Schrock, and G. A. Rupprecht, I. Arn. Chern. Soc. 103, 5752
(1981); (b) H. W. Turner and R. R. Schrock, I. Arn. Chern. Soc. 104,2331 (1982).
171. G. Fink, R. Rottler, and C. G. Kreiter, Angew. Makrornol. Chern. 96,1 (1981).
172. B. Rebenstorf and R. Larsson,!. Mol. Catal. 11, 247 (1981).
173. E. S. Novikova, V. S. Stroganov, and V. M. Frolov, Kinet. Katal. 22, 1480 (1981).
174. V. M. Akhmedov, A. A. Khanmetov, and A. G. Azizov, Zh. Org. Khirn.17, 1661 (1981).
175. R. B. A. Pardy and I. Tkatchenko, I. Chern. Soc. Chern. Cornrnun., 49 (1981).
176. P. W. N. M. Van Leeuwen and C. F. Roobeek, Tetrahedron 37, 1973 (1981).
177. I. Mochida, H. Okamoto, K. Kitagawa, H. Fujitsu, and K. Takeshita, Ind. Eng. Chern.
Prod. Res. Dev. 20,178 (1981).
178. J. G. Van Ommen, J. G. M. Van Rens, and P. J. Gellings, I. Mol. Catal.13, 313 (1981).
422
References
179. J. Levisalles, F. Rose-Munch, H. Rudler, J. C. Daran, Y. Dromzee, and Y. Jeannin, I.
Chern. Soc. Chern. Cornrnun., 152 (1981); J. Levisalles, F. Rose-Munch, H. Rudler, J.
C. Daran, Y. Dromzee, Y. Jeannin, D. Ades, and M. Fontanille, I. Chern. Soc. Chern.
Cornrnun., 1055 (1981); H. Rudler, F. Rose, M. Rudler, and C. Alvarez, I. Mol. Catal.
15,81 (1982).
180. B. L. Booth, R. N. Haszeldine, and I. Perkins, I. Chern. Soc., Dalton Trans., 2593 (1981).
181. c. L. Lee, C. T. Hunt, and A. L. Balch, Inorg. Chern. 20, 2498 (1981).
182. J. Chatt, Cherntech, 162 (1981).
183. c. J. Pickett and G. 1. Le,igh, I. Chern. Soc. Chern. Cornrnun., 1033 (1981).
184. (a) R. A. Henderson, I. Chern. Soc., Dalton Trans., 917 (1982); (b) I. Organornet. Chern.
208, C51 (1981).
Author Index
The page on which an author is cited is given first, followed by the reference number(s) in
parentheses.
Abboud, W., 344 (Ill), 362 (96)
Abdel-Khalek, A. A., 70 (108)
Abdullaev, F. A., 360 (74)
Abel, E. W., 213 (148-150), 332
(66), 337 (81-86), 341 (100)
Abeles, R. H., 280 (22)
Abrams, M. J., 190 (23)
Abu-Shady, A. S. I., 227, 230 (69)
Achiwa, K., 365 (121)
Adamcikova, L., 101 (186)
Adams, D. M., 338 (89)
Adams, R. D., 345, 347 (121)
Adamson, A. W., 150 (47), 174
(85),209 (128),241 (21)
Addison, A. W., 29, 45 (63)
Ades, D., 375 (179)
Adeyemo, A., 198 (63)
Adzamli, I. K., 49 (114),50 (115),
51 (114-115), 59 (30)
Agaev, F. M., 360 (74)
Agarwal, S. c., 69 (101)
Agarwala, U., 203 (95)
Agmon, N., 10 (41)
Agostini, G., 316 (49),332 (60)
Ahmad, F., 61 (46)
Ahmed, M., 363 (98)
Ahmeti, X., 232 (102)
Ahn, B. T., 45 (66)
Aime, S., 343 (106), 345 (ll5)
(125), 346 (125), 348
(128-129)
Aka, K., 231 (94)
Akabori, K., 152 (61)
Akermark, B., 305 (16), 330 (51)
Akhmedov, Y. M., 374 (174)
Akhtar, M. J., 89 (69),90 (70) (75)
Akutagawa, S., 369 (145)
AI-Allaf, T. A. K., 297 (88)
Albers, M. 0., 242 (27-28), 243
(29-30)
Alberts, A. H., 19, 20 (71)
Albery, W. J., 49 (106)
Albin, M., 16 (Ill)
Albrich, J. M., 97 (131)
Albright, T. A., 328 (43), 329 (48),
332 (59)
Alcock, N. W., 108 (10), 119 (45),
128 (65), 261 (93), 322 (16)
Aldred, S. E., 87 (43)
Aleshin, Y. Y., 89 (68)
Ali, G., 148 (37)
Alison, J. M. c., 332 (63)
AI-Jibori, S., 130 (75), 289 (61)
AI-Kaabi, S. S., 87 (47)
Allen. A. 0., 55 (8)
Allen, G. H., 204 (107)
AI-Najjar, I. M., 305 (12)
AI-Omran, F., 85 (33)
Alper, H., 351 (5), 369 (148)
AI-Rubaie, A., 99 (154)
AI-Saigh, Z. Y., 248 (41)
AI-Shali, S. A. I., 81 (15)
AI-Shatti, N., 29, 32 (61), 44
(60-61),56 (15)
Alt, H. G., 326 (36)
Alvarez, c., 375 (179)
Alway, D. G., 343 (109)
Amer, S., 254 (61-62)
Amma, E. L., 305 (13)
Amorrath, K., 74 (144)
Anast, J. M., 59 (32). 98 (149)
Andersen, R. A., 254 (63)
Anderson, G. K., 130 (72), 264
(105), 322 (15), 354 (26)
Anderson, M. P., 354 (32)
Anderson, O. P .. 330 (52)
Anderson, S. N., 67 (83)
Anderson, T. J., 6 (24), 30, 32, 42
(43)
Andreetta, A., 353 (17a-c)
423
Andrews, M. A., 356 (45c), 360
(77)
Andrews, R. K., 161 (34)
Andrich, G., 355 (39)
Andriollo, A., 364 (113)
Angelici, R. J., 302 (4-5)
Angelis, C. T., 96 (116)
Angermann, K., 149, 150 (42),
173 (79-80)
Annibale, G., 117 (42), 121 (52)
Anson, F. c., 38 (27), 72 (127)
Antonini, E., 197 (61), 231 (95)
Antonopoulos, G., 197 (57)
Aoyagui, S., 21 (76)
Apostol, I., 360 (75a)
Appelman, E. H., 70 (105),99
(155-157), 103 (205)
Aprahamian, G., 51 (116)
Arewgoda, C. M., 254 (60)
Armentrout; P. B., 282 (32-33)
Armisted, C. R., 61 (47)
Armstrong, J. L., 208 (122)
Aronachalam, M. K., 28, 29, 37
(21)
Arshankov, S. I., 151, 152 (52-53)
Arthur, C. D., 99 (155)
Aruga, R., 195 (49)
Arzouyan, c., 368 (140)
Asali, K. J., 239 (16)
Ascenzi, P., 197 (61),231 (95)
Ashby, E. c., 285 (48)
.xshley, K. R., 173 (77)
Ashworth, T. Y., 201 (81). 242(28),
243 (30), 250 (51)
Askalani, P., 194 (47)
Asmus, K. -D., 95 (105), 97 (136)
Asperger, S., 133 (3), 232 (102)
Astakhova, N. N., 343 (105)
Astanina, A. A., 91 (81)
Astruc, D., 315 (45),317 (51)
424
Atkinson, L., 22 (106)
Atlay, M. T., 361 (79)
Attali, S., 358 (56)
Atton, J. G., 306,308(21),311 (33)
Atwood, J. D., 239 (14),255 (72)
(74), 258 (87), 259 (88-89),
362 (89)
Augustin, M. A., 29 (63), 45 (63)
(65)
Austin, R. H., 14 (112)
Aymonino, P. J., 191 (27)
Aziz, A., 87 (42)
Azizov, A. G., 374 (174)
Babac, A., 66 (81)
Babievskaya, I. Z., 209 (126)
Bachofer, S. J., 360 (69)
Backer-Dirks, J. D. J., 345, 347
(122)
Backvall, J. E., 361 (81)
Backx, C., 359 (65)
Badasyan, G. Y,. 360 (71)
Baer, C. D., 95 (108), 233 (113)
Bahneman, D., 96 (120), 97 (138)
Baierl, B., 189 (16)
Bailar, J. c., Jr., 170 (64)
Bailey, W. I., 339 (91)
Baillie, P. J., 84 (29)
Baiocchi, c., 226 (61), 227 (68)
Baird, M. c., 284 (40)
Bakac, 28 (17),37 (17-18),134 (6)
(8-9), 135 (6), 136 (8-9), 138
(9), 249 (45), 272-274 (5),274
10-12), 275 (12),281 (23)
Balahura, R. J., 175 (88)
Balakrishman, K. P., 6 (24)
Balakrishnan, B. P., 72 (128)
Balakrishnan, R., 61 (44)
Balan, M., 71 (110)
Balasubramanian, P. N., 28 (21),
29 (21-22), 37 (21), 38 (22)
Balazs, A. c., 293 (78)
Balch, A. L., 108 (11-12),131 (76),'
375 (181)
Balcsllbramanian, K. P., 30, 32,
42 (43)
Baldwin-Zuschise, B. J., 258
(84-85)
Bali, A. S., 208 (123)
Ball, R. G., 365 (122)
Ball, S. S., 96 (117)
Balon, M., 101 (169)
Balschi, J. A., 90 (75)
Bait, S., 108 (9), 109 (14), 163 (39),
206 (113), 207 (116-117), 208
(124)
Balzani, Y., 5 (21),10(45),151 (49)
Banas, B., 53, 54 (I)
Bando, K., 355 (35)
Banerjea, D., 144 (22), 160 (27),
225 (44), 228 (78)
Banerjee, P., 73 (140),96 (125),
97 (141), 107 (7), 160 (27)
Banerji, K. K., 65 (74)
Banks, R. L., 370 (151)
Bannister, C. E., 224, 225 (42-43)
Banville, D. L., 102 (199)
Bar, 1.,43 (51)
Baranetskaya, N. K., 317 (52)
Baraona, R., 73 (134)
Bardi, R., 354 (25)
Bardsley, J. N., 6 (93)
Barefield, E. K., 252 (56)
Bar-Eli, K., 71 (115), 101 (189),
102(191)
Bargarello, E., 48 (95)
Barghi, E. B., 59 (28)
Bark, L. S., 167 (55)
Barner-Thorsen, c., 343 (107)
Bartoszek-Loza, R., 202 (88)
Basak, A. K., 144 (22)
Basolo, F., 170 (68),237 (1-2),
243,244 (31), 255 (71) (75),
262 (94)
Basset, J. M., 344 (111),362 (96),
372, 373 (165)
Basson, S., 148 (36), 173 (76)
Basu, A., 202 (87)
Baswani, Y. S., 61 (46)
Battacharyya, S. N., 44 (55) (56)
Battioni, J. -P., 283 (38)
Baudry, D., 325 (24)
Bauer, P., 285 (45), 366 (133)
Bayoud, R. S., 311 (30)
Beattie, J. K., 9 (96), 170 (64), 223
(33)
Beauchamp, J. L., 282 (32-33)
Beaupere, D., 366 (133)
Beck, M. T., 87 (45),91 (80b), 177
(99)
Begbie, C. M., 158 (16), 165 (45)
Beier, B. F., 358 (53a)
Bellachioma, G., 249 (48),287 (54)
Bellagamba, Y., 352 (II)
Bembi, R., 26, 36(10), 37 (12),179
(104)
Bencheick, A., 372 (163)
Bencini, A., 44 (57)
Bencze, L., 371 (155)
Benfield, R. E., 342 (103)
Benn, R., 327 (39), 330 (52)
Benner, L. S., 358 (5Ib)
Bennett, M. A., 263 (104),333,334
(72)
Bennett, M. R., 92, 93 (83)
Ben Taarit, Y., 344 (III)
Bercaw, J. E., 268 (111),340 (95)
Berenblyum, A. S., 363 (103), 367
(138)
Bergkamp, M. A., 210 (130)
Bergman, R. G., 239 (10), 250(53),
260,261 (91), 265 (109), 269
(115), 288 (57), 292 (72)
Bernstein, J. S., 16 (57),43 (51)
Bernstein, R. B., 6 (94)
Bertero, L., 368 (144)
Bertolino, J. R., 192 (36)
Besse, J., 87 (55)
Author Index
Bezems, G. J., 237, 252 (4)
Bhaduri, L. M., 64 (62)
Bhaduri, S., 73 (133), 364 (110)
Bharadwaj, L. M., 64 (62)
Bhargava, S. K., 213 (148), 332
(66), 337 (85-86)
Bhatia, I., 65 (74)
Bhattacharaya, A. K., 94 (103)
Bhattacharjee, A. K., 74 (149), 79
(3)
Bhatiacharjee, M., 74 (149),79 (3)
Bhattacharya, M., 145 (28)
Bhatti, M. M., 337 (83)
Biagini-Cingi, M., 121 (52)
Bianchi, M . 351 (6)
Bianco, C. D., 367 (135)
Bickley, D. G., 324 (20)
Bied-Charreton, c., 282 (31)
Biehl, E. R., 311 (30)
Bielski, B. H. J., 55 (8), 95 (112),
201 (85)
Biersack, H., 345 (113)
Bifano, c., 151 (50)
Bignetti, L. P., 204 (105)
Bino, A., 16 (100),339 (91)
Binstead, R. A., 32 (74)
Binzet, N. S., 248 (41)
Birch, A. J., 310 (25-26) (28), 311
(28) (31)
Bird, P. H., 148 (38), 211 (137)
Birge, R. R., 96 (113)
Birk, J. P., 139 (10)
Birus, M., 64 (67)
Bischofberger, P., 321 (5)
Bisset, W. I. K, 192 (32)
Bixon, M., 8 (34), 9 (38)
Bjergbakke, E., 96 (118-119), 97
(133)
Blackborow, J. R., 356 (43), 358
(52a)
Blackburn, N. J., 55 (9-11), 361
(86)
Bladon, P., 332, 334 (70)
Blake, D. M., 289(59), 292(70-71)
Blakely, R. L., 161 (32-34)
Blakeney, A. J., 288 (55)
Blandamer, M. J., 69 (96), 107,
109 (8),195 (50),196(51-53),
206 (112), 208 (122), 249
(42)
Bleeke, J. R., 363 (105)
Blenkers, J., 329 (49)
Blesa, M. A., 59 (28), 191 (27)
Blinn, E. L., 142, 146 (19)
Bloc, F., 100 (167)
Blum, A., 84 (28)
Blum, y., 366 (132)
Blunt, J. W., 159 (22), 160 (24)
Boehme, H., 177 (99)
Bogsanyi, D., 310 (25)
Boissonade, J., 101 (183)
Boland-Lussier, B. E., 325 (31)
Bolletta, F., 151 (49)
Bonivento, M., 116 (37-38)
Author Index
Bonner, F. T, 67 (87-88). 88 (58),
89 (65) (69), 90 (65) (70-71)
(75)
Bonnett, R., 87 (47)
Booij, M., 160 (26)
Booth, 8. L., 267 (110), 293 (75),
375 (180)
Booth, M., 213 (149-150),337
(81-82),341 (100)
Boreham, C. J., 179 (105), 180
(106)
Borgarello. E., 48 (97)
Borges, R. H. u., 196 (56)
Borghese, A, 81 (14)
Borghi, E. B., 191 (27)
Bortolini, 0., 360 (67-68)
Bose, R. N., 23, 24 (3)
Bosma, R. H. A., 372 (164).
Bosnich, 8., 351 (6), 364 (117),365
(124), 366 (125)
Bottcher, W., 47 (85), 174 (86)
Botteghi, c., 351 (6), 352 (II)
Boubel, J. c., 227 (73)
Boucher, H., 97 (139)
Bouder, H., 62 (52)
Boutonnet, J., 314 (40-41),315
(41)
Braca, G., 355 (39)
Brault, D., 283 (37)
Braun, AM., 48 (92)
Brauner, J., 225 (51)
Bremard. c., 201 (82), 205 (III)
Bresadola, S., 363 (101)
Briant, C. E., 130 (74)
Brickler, J. c., 343 (1 09),345 (118),
359 (61)
Briggs, J. R., 305 (74)
Brindley, P. 8., 247, 283 (35)
Brinkley, C. G., 129 (71)
Brisdon, B. J., 321 (7)
Brodovitch, J. c., 31, 43 (50), 44
(58)
Brookhart, M., 325 (26-28), 326
(28), 332 (59), 333, 334 (69)
(71)
Broomhead, J., 17 (66)
Broszkiewicz, R. K., 84 (28)
Brothers, P. J., 271 (2)
Brouwers, A M. F., 297 (89)
Brown, C. A., 337 (81)
Brown, D. A, 306, 308, 309 (22)
Brown, D. 8., 14, 22 (83),299 (96)
Brown, G. A, 142, 146 (19)
Brown, G. M., 92, 93 (83), 191
(29), 227 (75)
Brown, J. M., 324 (19), 362 (95),
364 (116)
Brown, K. L., 182 (114), 279 (19),
2S0 (20-21), 336 (77)
Brown, M. P., 341 (101)
Brown, T. L., 239 (14), 254 (64),
255 (64) (66-68)
Brownstein, S., 188 (5)
Brubaker, C. H., 42 (39)
Bruce, M. I., 253 (59), 288 (56)
Briickner, R., SO (5)
Brugger, P. A., 48 (92) (94)
Bruice, T c.. 96 (117)
Brummer, J. G., 101 (168)
Brunner, H., 263 (100-101),317
(50)
Brunori, M., 197 (61),231 (95)
Brunschwig,8. S., 7 (31),9 (31)
(37), II (49),49 (108), 191
(29), 227 (75)
Bryndza, H. E., 250 (53)
Buckingham, D. A., 155 (7), 159
(21), 164 (43), 175 (89), 179
(103) (105), 180 (106), lSI
(107-108) (111),182 (112)
Buckingham, M. J., 190 (20)
Budge, J. R., 72 (124)
Bueno, c., 345 (1 IS) (124), 347
(124)
Buhks, E., 8 (34), 9 (38)
Bukatov, G. D., 373 (16S)
Bulls, R., 289 (59)
Bunker, B. c.. 21 (79)
Bunton, C. A., 91 (79), 315 (46-47)
Burch, R. R., 331 (57)
Burchardt, D., 29, 39 (37)
Burdon, M. G., 192 (32)
Burgess, J., 69 (96), 107, 109 (8)
188 (6),194(45)(47),195(48)
(50), 196 (51-53), 197 (60),
206 (112), 208 (122), 249 (42)
Burnett, M. G., 168 (56)
Burrows, H. D., 193 (40)
Burton, c., 17 (66)
Busetto, L., 345 (123)
Bushnell, G. W., 110 (IS)
Busse, G., 217 (7)
Bustin, D. J., 139 (11)
Butler, A. R., 192 (32)
Butler, J., 49 (109-110),50 (109)
Butler, L. A., 49 (105)
Butler, S. E., 6 (92)
Butts, S. 8., 261 (93), 262 (95)
Buxton, Gr. Y., 49, 51 (114)
Byers, 8. H., 255 (66)
Cabelli, D. E., 201 (S5)
Calabrese, J. c., 293 (74)
Caldin, E. F., 225 (49), 233 (107)
Calfa, J. P., 88 (58)
Callahan, R. W., 18 (115),21 (73)
Calvaruso, G., 63 (56-57)
Cameron, J. H., 199 (66),231 (98)
Cameron, T. S., 341 (100)
Campbell, C. B., 74 (144)
Campello, c., 360 (68)
Camus, A., 366 (127) (134)
Cannon, R. D., 4 (11) (16), 6 (29),
16 (61), 20 (72), 22 (82), 58
(27b), 210 (134)
Canovese, L., 116 (37-39), 121 (52)
Capka, M., 362 (94)
Caplar, Y., 364 (115)
425
Cardaci, G., 249 (48), 287 (54)
Carlton, L., 361 (78)
Carr, C. M., 201 (80), 249 (49)
Carr, P. A G., 97 (132)
Carrasco, N., 315 (46-47)
Carta, G., 199 (70)
Casabo, J., 152 (60)
Casalavovo, A L., 354 (32)
Casal bore, G., 202 (89)
Casewit, c., 91 (78)
Casey, C. P., 239 (17),241 (24),
340, 341 (97), 356 (45c)
Cass, M. E., 256 (79)
Casula, M., 144 (23)
Cattalini, L., 116 (36-39): 117 (42),
121 (52)
Caulton, K. G., 283 (34), 337 (88),
339 (93), 356 (48), 366 (128)
Cavalieri, d'Oro, P., 353 (l7a-c)
Cavasino, F. P., 63 (56-57), 227
(66)
Cavinato, G., 354 (25) (30)
Cavoli, P., 354 (25)
Cayley, G. R., 228, 229 (80)
Ceccon, A, 316 (49), 332 (59)
Celap, M. B., 170 (64)
Cerney, M. T., 29, 42 (38)
Cesa, M. c., 239 (17)
Cesarotti, E., 351 (2), 364 (118)
Ceulemans, A., 210 (131)
Chakravorty, A, 16 (103-104)
Chalelpayil, P., 23, 24 (2)
Chalilpoyil, P., 204 (105)
Challis, B. c., 87 (46)
Chaloner, P. A., 336 (77), 362 (95),
364 (116), 365 (121)
Cham, M. S., 32, 46 (77)
Chambers, J. G., 196 (52),249(42)
Chan, M. S., 4 (13), 33, 48 (87)
Chan. S. -F., 33,48 (87),207 (119)
Chandra, G., 69 (101)
Chandrasekaran, K., 33, 47 (81)
Chandrasekharam, G., 68 (91),89
(63)
Chang, C. K., 231 (97)
Chang, C. - Y., 243, 244 (31)
Chang, J. c., 142 (17-18)
Chang, S. G., 88 (60), 90 (72), 227
(74)
Chang, T. C. T, 304 (10-11)
Chanon, M., 3 (7), 106 (4), 212
(146)
Chao, K., 328 (42)
Chapelle, S., 99 (154)
Chapman. R. D., 30 (45-46).31
(46), 43 (44- 46)
Charles, W. G., 305 (13)
Chase, D. 8., 368 (139)
Chatgilialoglu, c., 80 (7)
Chatt, J., 67 (83), 376 (182)
Chatterjee, c., 144 (22), 208 (123)
Chatterjee, Y., 65 (73)
Chaudhury, N., 252 (57)
Chauhan, S. M. S., 87 (50)
426
Che; C. -M., 49 (105), 203 (97)
Che, T. M., 224 (37)
Chen, M. M. L., 326 (33)
Chen, Y. -T., 243. 244 (31)
Chew, A., 208 (122)
Chew, Y., 198 (62)
Chieric.ato, G., 96 (115)
Chimatadar, S. A., 37 (20)
Chin, D. -H., 56 (20),96 (115)
Ching-Sung Hsiao, 194 (46)
Chipperfield, 1. R., 289 (60)
Cho, B. R., 364 (109)
Choi, H. S., 301 (1),306 (17)
Choi, H. W., 324 (23), 358 (53b)
Chojnowski, 1., 95 (104)
Chopra, S. K., 318 (55-56)
Christenson, 1. R., 353, 354 (l9b)
Chua, P. S., 365 (124)
Churchill, M. R., 325 (31), 335
(75),345 (118)(124), 347(124)
Cihova, M., 361 (84), 368 (142)
Cimolino, M. c., 150 (45)
Cinquantini, A., 130 (73)
Clack, D. W., 310 (29)
Clark, C. R., 159 (21), 163 (43),
175 (89), 179 (103), 181 (III),
182 (112)
Clark, H. c., 130 (72), 264 (IDS),
323 (17), 354 (22) (26)
Clark, H. W., 22 (84)
Clark, R. 1. H., 22 (86-87) (89)
Clark, S. F., 210 (132)
Clarke, M. 1., 203 (100)
Clear, 1. M., 202 (91)
Clive, G. M., 73 (137)
Cloninger, K. K., 18 (115)
Coates, J. H., 132 (79), 228 (79)
Codeman, W. M., 72 (126)
Coe, J. S., 113 (28-29), 114 (30a),
226 (54-55)
Coenen, 1. W. E., 362 (93)
Coffey, K. F., 203 (100)
Cohen, H., 38 (30), 133 (5)
Cohen, S., 16 (100)
Cole-Hamilton, D. 1., 202 (90)
Collamati, I., 198 (64)
Collings, P., 99 (151)
Collman, 1. P., 265 (107)
Colquhoun, H. M., 90 (77)
Comisso, G., 364 (115)
Connick, R. E., 98 (148), 145 (26),
230 (81)
Consiglio, G., 354 (27)
Constable, E. c., 201 (86), 333
(68), 345 (114)
Coolbaugh, T. S., 371 (156)
Cooper, M. K., 117, 118 (43),323
(18)
Copperthwaite, R. G., 291 (67)
Corden, B. D., 72 (131)
Cornelius, R. D., 176(90), 177(93)
Coronas, 1. M., 166 (49)
Corriu, R. J. P., 82 (21)
Cosmano, R., 210 (135)
Cossar, J., 100 (165)
Costa, G., 169 (62)
Costa, S. M. B., 249 (43)
Cotton, F. A., 16 (101), 189 (17),
239 (11-12), 247 (38),339 (91)
Cotton, 1. D" 259 (90), 262 (99)
Coville, N. 1., 242 (26-28), 243
(29-30)
Cox, B. G., 222 (26-28), 223
(29-31), 224 (35), 226 (57)
Crea, 1.,218 (115)
Creaser, I. I., 175 (87)
Creazzola de 0, F., 226 (52)
Creix, A., 139, 146 (14)
Crentz, c., 33, 48 (87)
Cresswell, P. 1., ISS (7)
Creswell, C. 1., 332 (65)
Creutz, c., II (47-48), 12 (47), 15
(107), 16 (64), 17 (67),33,34
(90), 46 (78), 48 (90), 55 (6)
Crisp, G. T., 259 (90), 262 (99)
Cristiani, F., 60 (36), 199 (70)
Crocker, c., 130 (75), 289 (61),
305 (14)
Cross, R. 1., 129 (70), 264 (106),
322 (15)
Crozet, M. P., 79 (2)
Csanyi, L. 1., 73 (138), 96
(122-123)
Cuccru, A., 289 (62)
Cuendet, P., 48 (94)
Cully, N., 315 (46)
Cummins, D., 49, 50 (107)
Curci, R., 360 (69)
Curtis, 1. c., 14 (109), IS (113), 16
(57), 39 (31)
Cushman, B. M., 299 (96)
Cusumano, 1. A., 356 (43)
Cusumano, M., 109 (15),114(31),
128 (64), 233 (110)
Cutler, A. R., 262 (97)
Cypryk, M., 95 (104)
Czakova, M., 362 (94)
Daffe, Y., 181 (110)
Daffner, G., 154 (5)
Dagdigian, 1. Y., 9 (97)
Dagnall, S., 217 (7)
Dalta, C. E., 61 (47)
Daly, Y. A., 259 (90)
Dani1ova, L. G., 363 (103)
Daran, J. c., 375 (179)
Darchen, A., 317 (5 I)
Darensbourg, D. J., 239 (11-13)
(15), 247 (37-38), 248 (39),
257 (81-82),258 (81) (84-85),
320 (1-2), 358 (57)
Darensbourg, M. Y., 239 (13), 241
(23), 247 (36), 286 (5 I), 320
(3), 358 (57)
Daroda, R. 1., 356 (43),358 (52a)
Das, S., 160 (27)
Dash, A. c., 98 (150), 157 (13),
163, 164 (42), 166 (SO), 172
(73) (75), 221 (19-20)
Dash, M. S., 157 (13)
Author Index
Dateo, C. E., 71 (120), 102 (200)
Datta, D., 16 (103-104)
Davidson, P. A., 61 (47)
Davies, D. M., 49 (109-110),50
(109) (115), 51 (115),100
(162), 20 I (80), 249 (49)
Davies, G., 57, 58 (27a), 66 (82),
188 (3)
Davies, J. A., 106 (2), 130 (72),264
(105), 354 (22) (26)
Davies, M. B., 167 (53-55)
Davies, S. G., 315 (42)
Davis, D. D., 83 (22)
Davis, M. A., 189 (15)
Davis, S. c., 285 (47)
Davison, A., 189 (II) (15), 190 (23)
Davoudzadeh, F., 315 (47)
Dawkins, G. M., 340 (96)
Day, A., 321 (7)
Day, C. S., 256 (77)
Day, P., 17 (65),22 (106)
Day, Y. W., 254 (63),256 (77),263
(102), 331 (57)
De, G. S., 145 (28)
De Brosse, C. W., 256 (79)
De Croon, M. H. J. M., 367 (93)
De Kepper, P., 71 (112-113)
(119-120), 100 (160), 101
(183) (190), 102 (190) (196)
(198) (200-201)
De Laive, P. 1., 50-51 (117)
De Liefdemeijer, H. 1., 329 (49)
De Lucca, G., 82 (20)
De Ochoa, O. L., 364 (I 13)
De Oliveira, L. A. A., 12, 13, 15
(53), 39 (35)
De Santis, de M. Y., 226 (52)
De Schteingart, L. M., 59 (28)
De Suarez, A. F., 190 (24)
De Waal, D. 1. A., 122 (53-54),
131 (54) (78), 201 (81), 250
(51),290(64-65),291 (66-67)
Des Abbayes, H., 315 (45)
Debreczeni, F., 230 (81-82)
(84-85)
Dedieu, A., 265 (108), 362 (91)
Deeming, A. J., 345 (119) (122),
347 (122), 348 (129)
Degani, H., 89 (69)
Deh, M. K., 336 (80)
Dekkers,l., 181 (108)
Delahay, P., 16 (59-60)
Delaver, M., 142 (16)
Dell, W., 268 (113-114)
Delpuech, 1. J., 218 (114),227 (73)
Demanet, C. M., 291 (67)
Demieva, M. M., 159 (20)
Demitras, G. c., 358 (53b)
Demmin, T. R., 361 (85a)
Deplano, P., 199 (70)
Derencsenyi, T. T., 364 (106)
Descotes, G., 362 (95), 365 (I 23a)
Deutch, 1., 285 (44)
Deutsch, E., 59 (30), 147 (34)
Devekki, A. Y., 361 (80)
Author Index
Devia, D. H., 217 (7)
Devillanova, F. A., 60 (36)
Devynck, J., 282 (31)
Dhur, A., 160 (27)
Di Cosimo, R., 124, 125 (59b), 297
(90-91),298 (91), 371 (157)
Di Furia, F., 360 (67-69)
Di Marco, P. G., 202 (89)
Diamond, S. E., 360 (76)
Dias, A. R., 249 (43)
Diaz, A., 199 (70)
Diaz, J. A., 158 (17)
Dickert, F. L., 231 (99),232
(99-100)
Dickson, D. P. E., 21 (75)
Dickson, J., 96 (116)
Didio, E., 227 (66)
Diebler, H., 224 (36)
Diefenbach, S. P., 286 (52)
Diekmann, S., 38 (23)
Dikshitulu, L. S. A., 60 (38-39),
68 (91), 89 (63), 99 (152-153)
Dilworth, J. R., 66 (82), 188 (3)
Dimmit, J. H., 184 (119),282 (27)
Din, K. U., 145 (27)
Dindi, S. N., 60 (39)
Dines, T. J., 22 (89)
Diversi, P., 289 (62)
Dixon, K. R., 110 (18)
Dixon, N. E., 161 (31-33)
Diza, A., 60 (36)
Dobson, B. c., 87 (54)
Dobson, G. R., 239 (16), 248 (41)
Dodd, H. T, 371 (158)
Dodgen, H. W., 132(79), 199(73),
220 (16), 228 (79)
Doeff, M. M., 200 (78),233 (108)
Doi, T., 93 (90)
Dokuzovic, Z., 232 (102)
Dolgoplosk, B. A., 371 (154)
Dolphin, D., 282 (30)
Dorfman, L. M., 255 (65)
Dorn, H., 342 (104)
Dotz, K. H., 240 (18), 303 (6)
Doughty, D. H., 354 (32)
Doughty, D. T., 68 (89)
Dowling, N., 14, 15 (116)
Downes, J. M., 117, 118 (43),323
(18)
Doyle, G., 354 (34)
Dozsa, L., 87 (45)
Drago, R. S., 21 (79),72 (131), 210
(135)
Drakenberg, T., 108 (13)
Draper, M. R., 86 (38)
Dreos-Garlatti, R., 169 (62)
Dromzee, Y., 375 (179)
Duatti, A., 190 (25-26)
Duce, P. P., 107, 109 (8)
Duffield, A J., 107, 109 (8), 196
(51-52), 249 (42)
Duffy, D. J., 199 (69)
Duffy, N. V., 199 (68)
Duonghoug, D., 48 (95) (98)
Dupuis, M., 326 (33)
Durout, P., 360 (66)
Durham, B., 5 (20),6 (24),29 (40),
30 (43), 31 (40), 32 (43), 33
(40), 42 (40) (43)
Duttera, M. R., 325 (25)
Dyke, A. F., 341 (98)
Dziobkowski, C. T, 14, 22 (83)
Eaborn, c., 81 (10- I 3) (15), 297
(88)
Eady, D. T., 110 (18)
Earley, J. E., 23 (1-3),24 (1-6),36
(5-6),204 (104-105)
Eberson, L., 3 (6)
Eckelman, W. c., 189 (10)
Eddowes, M. J., 49 (106)
Edelson, D., 101 (177) (179)
Eden, D., 219 (10)
Edgard, B. L., 199 (69)
Edidin, R. T, 348 (127)
Edmonds, S. E., 203 (100)
Eduok, E. E., 361 (85b)
Edwards, D. S., 252 (56)
Edwards, J. 0., 95 (108), 155 (8),
233 (113), 360 (69)
Egolf, T., 341 (99)
Eguchi, T., 344 (110)
Eid, A. E., 166 (47)
Eidem, P. K., 352 (7)
Eiki, T, 94 (96)
Eisenhut, M., 189 (13)
Eisenstein, 0., 304, 310 (9), 371
(156)
Ekstrom, C. G., 230 (88)
EI-Awady, A. A., 60(33), 98(150),
171 (72), 172 (73-74)
EI-Ezaby, M. S., 227, 230 (69)
EI-Nasr, M. S., 168 (60)
EI'Natanova, A. I., 363 (102)
EI-Shafey,o. H., 73(139), 96(127)
Elding, L. I., 57, 58 (26-27), 10 I
(172), 108 (13), 128 (67-68)
Elgy, C. N., 225 (50)
Elias, H., 232 (103-106)
Eller, P. G., 268 (112)
Ellis, W. R., 178 (100)
Ellison, G., 87 (48)
Emmi, S., 48 (88)
Emuii, S. S., 27, 37 (15)
Endicott, J. F., 5 (20), 6 (24), 29
(40),30 (43), 31 (40),32 (43),
33 (40), 42 (40) (43), 72 (128),
170 (70)
Endo, M., 101 (180)
Engelhardt, G., 84 (25)
Englehardt, J., 371 (155)
English, A. M., 50, 51 (117)
Ephritikhine, M., 325 (24)
Epstein, I. R., 68 (90),71 (112-113)
(119-120), 100 (160), 101
(190), 102 (190) (196)
(198-201), 103 (202), 197 (59)
Epstein, J. R., 89 (64)
Ercolani, c., 197 (61),231 (95)
Ercoli, R., 352 (11)
Erdodi, F., 230 (82)
Eriks, K., 203 (100)
Eriksen, T. E., 100 (158)
Ermakov, Yu. I., 373 (168)
Espenson, J. H., 28 (17), 37
427
(17-18),66 (80-81),71 (123),
75 (151), 133 (4), 134 (6-9),
135 (6-8), 200 (75), 249
(45-46), 272 (4-5), 273 (5),
274 (5) (9-13), 275 (12-13),
276 (15), 281 (23)
Ettel, M. L., 55, 56 (13), 94 (98)
Evan, H., 59 (31)
Evans, D. J., 311 (34), 314 (39)
Evans, J., 345 (120)
Evgen'eva, I. I., 230 (83)
Evmenenko, N. P., 360 (74)
Ewen, 1. A., 247 (37)
Ezerskaya, N. A, 203 (101)
Fabian, 8. D., 331 (55)
Fabrizzi, L., 44 (57)
Fachinetti, G., 356 (47)
Fackler, J. P., 123 (56)
Fackler, J. P., Jr., 332 (63)
Fagan, P. J., 325(25), 340, 341 (97)
Fahey, D. R., 357 (50)
Fallab, S., 171 (71)
Faller, J. W., 328 (42)
Fanchiang, Y. -T., 43 (49),281 (24)
(26)
Farber, H., 223 (32)
Farina, R. D., 5 (18-19)
Farley, M. E., 67 (83)
Farnham, W. B., 82 (18)
Farver, 0., 51 (118)
Fastrez, J., 181 (110)
Faulkner, I. R., 254, 255 (64)
Fauvarque, J. -F., 295 (82)
Favez, R., 120 (46), 322, 323 (12)
Fawcett, J., 188 (6-7)
Fealey, T., 204 (104)
Feasey, N. D., 343 (108)
Fedorov, V. S., 361 (80)
Feinberg, 8. A, 51 (116)
Felkin, 325 (24)
Fellmann, F. D., 335 (74)
Fellmann, J. D., 352 (9), 374 (I 70a)
Fendler, J. H., 48 (93)
Fenske, R. F., 303 (7)
Ferraro, J. R., 21 (77)
Ferrer, M., 139, 146 (14), 166 (49)
Feser, R., 113 (27)
Field, J. P., 233 (107)
Field, R. J., 101 (168)
Fielding, P. E., 72 (125)
Fife, P. c., 101 (178)
Fikrig, E., 56 (22)
Filatova, L. S., 313 (36-37)
Fink, G., 374 (17)
Finke, R. G., 265 (107), 300 (98)
Finzel, R. 8., 83 (23)
Firman, P., 222 (28), 223 (30), 224
(35), 226 (57)
Firsich, D. W., 284 (41)
428
Fischer, H., 240(18-19),269(116),
303 (6), 353 (15)
Fleischer, E. B., 30 (45-46), 31
(46),43 (44-46)
Fleming, W., 178 (102)
Fletcher, P. D. I., 225 (46)
Flood, T c., 261 (92), 325 (26)
Floryan, Lilvberg, E., 57, 58 (25),
101 (175), 196 (54)
Flowers, L. I., 354 (28a)
Foa, M., 355 (37)
Foffani, A., 250 (52)
Folcher, G., 363 (104)
Foley, H. c., 256 (78)
Folting, K., 356 (48)
Fontanille, M., 375 (179)
Fontecave, M., 283 (38)
Foote, C. S., 95 (109-110)
Ford, P. c., 173 (78),210
(129-130) (133), 211 (133),
238 (8), 352 (13), 358 (54),
359 (60)
Foreman, T K., 256 (77)
Forni, L., 96 (120)
Forster, D., 352 (12)
Fox, A., 255 (69)
Fox, J. R., 256 (77)
Foxman, B. M., 164 (43), 304 (10)
Frahan, J., 38 (23)
Francalanci, F., 355 (37)
Francis, D. J., 179 (105)
Fninco, D. W., 200 (76-77)
Frankel, R. B., 19, 21 (74)
Franklin, K. J., 189 (12)
Franks, S., 289 (60), 296 (87), 353
(19c)
Fraser, A. J. F., 332 (63)
Frediani, P., 351 (6)
Freeman, F., 61 (47)
Freiberg, M., 29, 45 (63)
Frese, K. W., 4 (17)
Fresnov, M. A., 106 (I)
Frew, A. A., 341 (101)
Friar, M. J., 182 (112)
Friedman, H. A., 189 (14)
Friedman, H. L., 4 (9)
Friedman, R. M., 365 (120)
Friedrich, E. C., 82 (20)
Frohn, U., 232 (105)
Frolov, V. M., 363 (102),374
(173)
Fronabarger, J. W., 178 (102)
Fryzuk, M. D., 351 (6)
Fuchikami, T, 353 (20)
Fuchita, Y., 336 (78)
Fujimoto, M., 182 (113)
Fujitsu, H., 364 (IlIa-b), 375
(177)
Fujiwara, K., 85 (33)
Fukuda, R., 150 (47)
Fukutomi, H., 188 (2), 227 (63),
230 (89)
Funabashi, K., II (99)
Funahashi, S., 168 (57), 230 (91)
(93)
Funaki, Y., 224 (40)
Funke, L. A., 274, 275 (13)
Fuochi, P. G., 27, 37 (15)
Furrow, S. D., 71 (116-118), 102
(192-195)
Furuichi, R., 97 (134)
Fuselier, C. 0., 61 (47)
Gabrielyan, S. M., 360 (71)
Gaevskii, V. F., 360 (74)
Gafney, H. D., 33,47(83),202(87)
Gage, L. D., 189 (17)
Gagne, R. R., 20 (70)
Gainsford, A. R., 160 (24), 177 (95)
Gainsford, G. J., 164 (43)
Gaizer, F., 219 (II)
Gajda, G. J., 371 (156)
Galbacs, Z. M., 73 (138), 96
(122-123)
F., 210 (136)
Galuska, A. A., 59 (31)
Gamba, A., 352 (II)
Gambaro, A., 316 (49), 332 (60)
Gamidov, A. F., 91 (81)
Ganapathisubramanian, N., 96
(130), 10 I (185)
Gandler, J., 302 (3)
Gandolfi, M. T, 10 (46)
Garcia- Rosas, J., 222 (26-27), 223
(29) (31)
Gard, D. R., 254, 255 (64)
GarJey, M., 99 (151)
Garley, M. S., 88 (59)
Garmestani. S. K., 5 (18)
Garten, R. L., 356 (43)
Gashimov, A. G., 360 (74)
Gatehouse, B. M. K., 72 (124)
Gaudemer, A., 282 (31)
Gaul, J. H., 72 (131)
Gausing, W., 330 (52)
Gaydou, E., 368 (140)
Gazzola, c., 161 (32-33)
Geary, P. J., 21 (75)
Gebicki, J. M., 95 (112)
Geiseler, W., 71 (115), 101 (189)
Gelerinter, E., 62 (48)
Geletii, Yu V., 360 (74)
Gell, K. I., 286 (50)
Gellings, P. J., 375 (178)
Gemmill, J., 264 (106)
Gennaro, M. c., 230 (96)
Gentile, R., 356 (40)
Geoffroy, G. L., 256 (77-79), 356
(46)
Gerber, T. I. A., 122 (53-54), 131
(54) (78), 290 (64-65), 291
(66-67)
Gerger, T., 72 (127)
German, E. D., 4 (8)
Ghanbi, N., 15, 21 (80)
Ghazi-Bajat, H., 89 (66), 166 (48)
Ghilardi, C. A., 332 (61)
Ghoshal, A., 168 (58-59)
Giacomelli, A., 106 (6)
Giacomelli, G., 368 (144)
Author Index
Gibson, D. H., 328 (41)
Gibson, V. c., 363 (99)
Giegerich, G., 232 (105)
Giffney, J. c., 85 (32-33)
Gilfillan, W. M., 168 (56)
Gillard, R. D., 199(67),212(143)
(145) (147), 336 (79)
Gillie, A., 127 (63)
Giordano, R., 29, 39 (36)
Giro, G., 202 (89)
Girolami, G. S., 254 (63)
Gjerde, H. B., 276 (15)
Gladfelter, W. L., 256 (77)
Gladiali, S., 351 (6), 352 (II)
Gladysz, J. A., 288 (55), 325
(29-30), 326 (30), 356 (45a)
Glass; W. K., 306, 308, 309 (22)
Glavas, M., 168 (60)
Glavincevski, B., 188 (5)
Glenister, J. F., 57, 58 (27a)
Glick, M. D., 6 (24), 30, .12, 42 (43)
Glidewell, c., 192 (32)
Gobetto, R., 348 (128)
GobI, M., 97 (136)
Goddard, W. A. III, 371 (159)
Goel, A. B., 129 (71)
Goel, S., 129 (71)
Gold, V., 272 (6)
Golding, B. T, 185 (121)
Goldschmidt, J. M. E., 94 (100)
Golinelli, A., 10 (46)
Goncharov, A. A., 103 (204)
Goodwin, H. A., 194 (44)
Gordon, G., 68 (89), 230 (92)
Gosselink, J. W., 297 (89)
Gould, E. S., 24 (100), 25
(100-101),26 (100),27
(100-101),33 (101), 34 (100),
35 (100-10 I), 48 (100- J 0 I),
41 (48), 61 (42),62 (48-51),93
(89)
Gould, R. 0., 332 (63)
Gower, M., 201 (80), 249 (49)
Gowland, R. J., 91 (82)
Gragor, N., 361 (82)
Graham, D. R., 73 (136)
Graham, W. A. G., 249 (47), 292
(73), 331 (56), 356 (44)
Grancicova, 0., 158 (15)
Granger, P., 99 (154)
Grant, J. L., 100 (160)
Grant, M., 199 (72), 220 (14)
Grant, M. W., 226 (90)
Graser, B., 366 (130)
Grate, J. H., 182(115),279(17-18)
Grate, J. W., 279 (18)
Gratzel, M., 48 (92) (94-95),
(97-98), 352 (7)
Gray, H. B., 49 (102-105) (107), 50
(107) (113) (117), 51 (113)
(117),170 (67),352 (7)
Graziani, M., 367 (136)
Green, M., 169 (62), 305 (12), 340
(96), 345 (116-117) (123)
Green, M. A., 339 (93), 366 (128)
Author Index
Green, M. L. H., 315 (42),360 (72)
Greenwood, R. c., 225 (49)
Gregorio, G., 353 (17a-c)
Gregory-Jackson, W., 169 (61)
Gregson, A. K., 72 (125)
Grenthe, I., 230 (88)
Gress, M. E., 17 (67), 46 (78)
Gribschaw, T. A., 102 (199)
Griffith, E. A. H., 305 (13)
Grishin, Yu. K., 343 (105)
Grobe, J., 240 (20)
Groning, A B., 57, 58 (26), 128
(67)
Groning, 0., 57, 58 (27), 108 (13),
128 (67)
Gross, D. c., 359 (60)
Grove, D. M., 120 (48)
Grubbs, R. H., 371 (156), 372, 373
(167)
Grundy, K. R., 262 (96)
Guardado, P., 71 (110),101 (169)
Guerin, c., 82 (21)
Guglielmo, G., 114 (31), 128 (64),
223 (110), 355 (39)
Guimon, c., 318 (54)
Guindy, N. M., 73 (139), 96 (127)
Gupta, A. K., 61 (43)
Gupta, S. S., 68 (94), 69 (95), 93
(88), 97 (140)
Gupta, Y. K., 61 (43), 68 (92-94),
69 (95) (98), 70 (106), 93 (88),
95 (106-107), 97 (140)
Guthrie, J. P., 100 (165)
Haake, P., 94 (97)
Haber, J., 360 (75a)
Hadi, D. A., 132 (79), 228 (79)
Haelg, P., 354 (27)
Haim, A., 4 (12), 12 (53), 13 (53)
(56), 14 (108), 15 (53) (56), 38
(29), 39 (32-35), 40 (29)
(32-33), 41 (34), 47 (84-85),
174 (86)
Haines, R. I., 44 (58), 211 (141)
Halko, D. J., 282 (30)
Halpern, 1.,183(118),271 (I), 276
(14),277 (14) (16), 278 (14),
286 (52), 362 (92), 365 (124)
Hamann, C. A., 20 (70)
Hambright, P., 198 (63)
Hamilton, R., 361 (83)
Hamlin, J. E., 363 (99)
Hamshere, S. J., 107, 109 (8), 206
(112)
Hanckel, J. M., 241 (23), 247 (36),
286 (51)
Hancock, W. S., 181 (III), 182
( 112)
Hankey, D. R., 345 (117)
Hanna, A, 101 (197)
Hansen, P. 1., 139 (10)
Hanson, B. E., 342 (104)
Hanson, H. J., 321 (5)
Harada, S., 224 (40)
Harbour, 1. R., 91 (80)
Hardcastle, K. 1.,343 (107)
Harding, D. R. K.,181 (111),182
( 112)
Harlow, R. L., 82 (18)
Harmalker, S. P., 15,22 (81)
Harmer, M. A., 31,45 (70)
Harris, G. M., 60 (33), 98 (150),
163-164 (42), 167 (51), 171
(72), 172 (73-75), 207 (119),
221 (19-20)
Harris, R. K., 84 (24)
Harris, S. H., 290 (63)
Harsy, S. G., 241 (24),356 (45c)
Hart, E. 1.,96 (118-120), 97 (138)
Hartley, F. R., 106(2-3),289(60),
296 (87), 326 (35), 353 (19c)
Haruta, K., 96 (121)
Hasso, S., 345 (119)
Hastings, J. B., 9 (36)
Haszeldine, R. N., 293 (75), 315
(44),375 (180)
Hatterer, A., 100 (167)
Hatton, P. D., 338 (89)
Hawkes, G. E., 190 (20)
Hay, P. J., 326 (34)
Hay, R. W., 107 (7), 144 (22), 153
(I), 155 (10), 163 (38)(40),164
(44),179 (104), 181 (109)
Hayashi, T., 353 (18), 354 (23)
Heaton, B. T., 344 (110) (112)
Hegedus, L. S., 330 (51)
Heimbach, P., 351 (4)
Heinekey, D. M., 331 (56)
Heistand, R. H., 56 (21-22)
Heitner-Wirguin, c., 16 (100)
Hellmann, S. W., 231 (99),232
(99-100)
Helsby, P., 85 (34-35)
Hemmes, P., 225 (51)
Henderson, R. A, 66 (82), 67 (84),
90 (76), 162 (37),188 (3), 376
(184a)
Hendriksen, D. E., 90 (74)
Hennig, H., 79 (I)
Henrick, K., 345 (119)
Henrici-Olive, G., 358 (51 a), 373
(168)
Henry, B., 227 (73)
Henry, P. M., 14, 15(116),361 (82)
Hermann, H. J., 189 (13)
Herrick, R. S., 326 (38)
Herrmann, W. A., 345 (113), 356
(43)
Herschberger, 1., 284 (42)
Hersham, A, 352 (12)
Hershberger, J. W., 237, 245, 246
(6-7)
Hertli, L., 226 (53)
Herzschuh, R., 79 (I)
Hessley, R. K., 182 (114),280 (20)
Hessner, B., 345 (123)
Hester, R. E., 22 (85)
Heyward, M. P., 74 (142-143), 96
(126)
Hicks, C. P., 110 (17)
429
Hicks, J. R., 225 (45)
Hidai, M., 356 (43)
Higashimura, T., 10 (44)
Higashino, T., 82 (16)
Higginson, W. C. E., 37 (14), 71
(122),100 (161)
Hill, H. A. 0., 49 (106)
Hill, R. H., 131 (77),299 (97)
Hiller, K. -0.,97 (136)
Hillman, A. R., 49 (106)
Hinenoya, M., 372, 373 (166)
Hirai, K., 363 (99)
Hiraishi, M., 226 (62)
Hiraki, K., 336 (78)
Hiraki, M., 364 (108)
Hirose, Y., 300 (98)
Hirotsu, K., 72 (132)
Hobbs, c. F., 354 (29)
Hoebbel, D., 84 (25)
Hofer, E., 188 (4)
Hoffman, B. M., 16 (105)
Hoffman, G. A., 344 (110)
Hoffman, M. Z., 3 (3),27,37 (15),
48 (88-89), 149 (41), 151 (48)
Hoffmann, R., 125 (60), 293 (77),
294 (79),295 (77), 304, 310(9),
371 (156)
Hoffmann, W .. 328 (45)
Hoharum, M., 87 (42)
Ho1ba, V., 145(31), 158(15)
Holcman, J., 96 (118-119)
Holecek, D. R., 358 (52b)
Hollaway, M. R., 73 (137)
Holloway, C. E., 200 (79), 233
(109)
Holm, R. H., 19,21 (74)
Holmes, R. G. G., 293 (75)
Holt, E. M., 261 (93)
Holton, J., 113 (26)
Holwerda, R. A., 55, 56 (13-14),
94 (98)
Holzbach, W., 188 (4)
Hopfield, 1. 1., 6 (25), 14 (112)
Horvath, L., 73 (138), 96 (122)
Hoshino, M., 95 (III), 282 (29)
Houlding, V. H., 174 (85)
Hounslow, A. M., 221 (25)
House, D. A., 143 (20), 151 (56),
152(57),155(10),159
(22-23), 160 (24), 163 (38)
Hovis, F. E., 97 (132)
Howard, J., 329 (47)
Howard, 1. A. K., 345 (116) (123)
Howard, T. R., 371 (156)
Howard-Lock, H. E., 189 (12)
Howarth, O. W., 209 (125),251
(54), 333, 334 (73)
Howell, J. A. S., 348 (130)
Hoyano, J. K., 292 (73)
Hoyer, E., 73 (135), 96 (128)
Hrusousky, M., 368 (142)
Hsieh, L. -S., 101 (176)
Hsu, W. -L., 328 (41)
Hubbard, C. D., 195 (48)
Hubbard, L. M., 96 (113)
430
Huber, H., 88 (57)
Huchital, D., 151 (55)
Huchital, D. H., 29, 42 (41)
Hudson, J. L., 101 (181)
Huffman, J. c., 287 (53), 339 (93),
340 (94), 356 (48), 366 (128)
Hug, R., 257 (80)
Huggins, J. M., 239 (10),265 (109)
Hughes, M. N., 67 (86), 91 (80a),
92, 93 (84)
Hughes, O. R., 354 (2Ia-b)
Hughes, R. P., 325 (31)
Huisgen, R., 177 (97-98)
Hull, W. E., 84 (24)
Humphrey, M. B., 333, 334 (71)
Hung, Yann, 204 (106)
Hunold, H. -P., 171 (71)
Hunt, C. T, 108 (11-12),131 (76),
375(181)
Hunt, J. P., 132 (79),199 (73),220
(16), 228 (79)
Hurst, J. K., 97 (131-132)
Hursthouse, M. B., 345, 347 (122)
Husk, G. R., 325 (27-28), 326 (28)
Hussein, F. M., 306, 308, 309 (22)
Hwang, W. S., 31, 43 (47), 282 (28)
Hyde, K. E., 57, 58 (27a), 207 (120)
Hynes, M. J., 318 (55)
ladevia, R., 23, 24 (I)
Ibaraki, T, 82 (19)
Ibers, J. A., 16 (105), 124, 125
(59b)
Ige, J., 32, 46 (76), 193 (40)
Iida, M., 160 (25)
Ikariya, T., 371 (156)
Ikeda, F., 93 (90)
Ikeda, M., 360 (70)
Ikeda, T, 38 (28)
Ikeda, Y., 188 (2), 230 (89)
Illiminat, G., 144 (23)
Imamura, M., 95 (III), 282 (29)
Imanaka, T., 364 (lOS)
Imyanitov, N. S., 353 (15)
Inamo, M., 168 (57), 230 (91)
Incorvia, M. J., 257 (82)
Inczedy, J., 73 (135), 96 (128)
Indelli, M. T, 10 (45-46)
Indrayan, A. K., 68 (92-93), 70
(106), 95 (106--107)
Infelta, P. P., 48 (92)
Ingold, C. F., 65 (75), 66 (76)
Ingold, K. U., 80 (7)
I ngrosso, G., 289 (62)
Innocenti, P., 332 (61)
Innorta, G., 250 (52)
Inoue, T, 224 (39)
lonannou, P. v., 185 (121)
Ip, D. P., 99 (155)
Irish, D. E., 86 (39)
Ise, N., 159 (19)
Ishihara, K., 168 (57),230(91)(93)
Isobe, K., 123 (55a-b), 321 (10)
Isoyama, T, 354 (23)
Issler, S. L., 91 (80)
Istuzu, K., 59 (29)
Itabashi, M., 204 (103)
Ito, K., 82 (19)
Ito, T., 125, 127, 128 (61), 295(84),
322 (13)
Ito, Y., 10 (44), 189 (8),233 (112)
Itoh, K., 204 (103)
Itoh, T., 361 (87)
Ivin, K. J., 371 (160), 372 (164)
Iwamoto, K., 101 (184)
Izumi, T, 369 (148)
lzumitani, T, 54, 55 (4)
Jablonski, B., 177 (99)
Jablonski, C. R., 263 (103)
Jackson, R. A., 256 (76)
Jackson, W. G., 89 (67), 155 (7),
157 (II), 158 (16), 161
(30-31), 165 (45)
Jacocks, H. M., 83 (22)
Jafri, J. A., 9 (95)
Jallabert, c., 361 (8S)
James, B. R., 361 (79), 365 (122)
Jameson, R. F., 55 (9-11), 361 (86)
Jamieson, M. A., 27, 37 (15), 14S
(38), 149 (41), 151 (48)
Janik, T S., 362 (89)
Jannon. G., 348 (129)
Janowicz, A. H., 250 (53), 288 (57),
292 (72)
Jaoven, G., 342 (102),346 (126),
349 (102)
Jardine, F., 271 (3)
Jawad, J. K., 113 (25)
Jeannin, Y., 375 (179)
Jedral, W., 223 (30)
Jeffrey, J. c., 263 (104), 338 (90),
345 (123)
Jelsma, A., 206 (113), 207
(116-117), 20S (124)
Jencks, W. P., 280 (22)
Jenkins, H. D. B., 206 (112)
Jennings, P. W., 369 (146)
Jensen, J., 261 (92), 325 (26)
Jha, S. K, 69 (101)
Jimenez, P., 241 (23), 286 (51)
Jitsukawa, K., 361 (87)
Johannsen, B., 189 (9), 190 (22)
Johansson, I., 84 (30)
John, G. R., 302 (2), 309 (23-24)
Johnson, B. F. G., 237 (3), 342
(103),345 (114)
Johnson, B. Y., 328 (41)
Johnson, C. E., 243 (31), 244
(31-32), 321 (6)
Johnson, E., 282 (30)
Johnson, K. H., 293 (78)
Johnson, M. K., 22 (82), 61 (47)
Jonas, J., 344 (110)
Jones, A. G., 189(11)(15), 190(23)
Jones, A. J., 221 (23)
Jones, G. H., 74 (146)
Jones, N. K., 59 (31), 61 (47)
Jones, P., 100 (162)
Jones, R. D., 170 (68)
Author Index
Jones, R. F., 202 (90)
Jones, S. E., 56 (20)
Jones, W. D., 239 (10), 241 (24),
356 (45c)
Jones, W. M., 325 (32)
Jones-Parry, R., 87 (44)
Jordan, R. B., 25, 26, 36 (9), 155 (6)
(9), 199 (72),220(14),224(38)
Jortner, J., 8 (34), 9 (38)
Joshi, B. c., 61 (43)
Jungmann, H., 124 (58)
Jutland, A., 305 (16)
Kaden, T A., 226 (53), 228 (78)
Kai, E., 160 (25)
Kajihara, Y., 330 (53)
Kalatzis. E., 87 (51-52)
Kalinkin, M. I., 364 (ll4a-b)
Kamalov, G. L., 360 (71)
Kampmeier, J. A., 290 (63)
Kanai, H., 362 (90)
Kaneda, K., 361 (87) (108)
Kane-Maguire, L. A. P., 201 (80),
249 (49),302 (2),306 (18-21),
307 (18-20),308 (21),309 (21)
(23-24),310 (29),311 (33-34),
314 (39)
Kanluen, R., 256 (76)
Kaplan, E. B., 206, 208 (114)
Kaplan, L., 351 (2)
Karchesfki, E. M., 61 (47)
Karel, K. J., 257 (83), 332 (59)
Karlin, K. D., 29, 45 (63)
Kaspar, J.. 367 (136)
Kassim, A. Y., 70 (107), 10 I (170)
Kastner, M. E., 203 (100)
Katahira, D. A., 345, 347 (121)
Katakis, D., 64 (65), 274 (S), 317
(53)
Kath6, A., S7 (45)
Katsaros, N., 64 (65), 274 (8),317
(53)
Katsuki, T, 360 (70)
Kawabata, Y., 354 (23) (2Sa)
Kawaguchi, S., 114 (33-35), 115
(33), 119 (33-35) (44), 122
(53), 123 (55b), 189 (8),233
(112),321 (10)
Kawczynski, L., 364 (107)
Kazbanova, T K., 211 (142)
Kaslauskas, R. J., 244 (33)
Kazmi, S. A., 230 (90)
Keene, F. R., 61 (40),175 (87), 201
(84)
Kegley, S. E., 325, 326 (2S)
Kehoe, D. c., 253 (59)
Keijsper, J., 339 (92)
Keister, J. B., 356 (40)
Keith, D. D., 366 (126)
Keller, A. D., II, 12 (47), 33, 34,
48 (90)
Keller, H. J., 16 (102), 100
(162-163)
Kelly, I. D., 22S, 229 (SO)
Kelly, J. M., 202 (91)
Author Index
Kelly, K. P., 360 (77)
Kelly, L. F., 310 (25)
Kelly, R. P., 87 (53)
Keirn, H., 38 (24), 89 (66), 106 (5),
149, 150 (42),153 (2),154(5),
166 (48), I73 (79-80), 207
(118) (120),208 (118) (121),
230 (87)
Kelso, M. T., 223 (33)
Kemmerich, T., 177 (99)
Kemmitt, R. D. W., 336 (80)
Kemp, T J., 61 (41), 128 (64-65),
226 (58)
Kenley, R. A., 84 (27)
Kennedy, S., 345 (118)
Kent, A. G., 324 (19),362 (95),365
(123a)
Keppler, B., 16 (102)
Kermode, N. J., 113 (26)
Kerrison, S. J. S., 110(16)
Khalikova, N. U., 313 (37)
Khalil, M. I., 87 (42)
Khan, A. H., 71 (122), 100 (161)
Khan, A. R., 337 (84)
Khan, H. M., 44 (59)
Khan, I. A., 145 (27)
Khanmetov, A. A., 374 (174)
Kida, S., 96 (124), 174 (82)
Kidd, R. G., 190 (21)
Kido, H., 188 (I), 190 (19)
Kiel, W. A., 325, 326 (30), 356
(45a)
Kii, N., 361 (87)
Kiji, J., 363 (100)
Kikkawa, E., 26, 37 (13)
Kildahl, N. K., 197 (57)
Kim, H. O. A., 49, 51 (114)
Kim, L., 354 (24)
Kimura, E., 132 (80)
Kimura, M., 5 (23), 54, 55 (5), 56
(17-18), 100 (164)
King, A. D. Jun., 358 (55) (58)
King, D. L., 356 (43)
King, G., 213 (149)
King, R. B., 358 (55) (58)
Kinne, M., 353 (15)
Kira, A., 10 (43)
Kirk, A. D., 149 (40), 150 (44)
Kirker, G. W., 272, 273, 274 (5)
Kirkes, G. W., 134, 135, 136 (8)
Kishi, K., 362 (90)
Kiss, M .. 368 (142)
Kisslinger, J., II (54), 13, 14
(54-55),48 (91)
Kitagawa, K., 375 (177)
Kitamura, T, 82 (16)
Kitaura, K., 293 (76)
Kite, K., 213 (148), 337 (84-86)
Kiwi, J., 48 (97)
Kizas, O. A., 343 (105)
Klabunde, K. J., 285 (47)
Kliining, U. K., 10 I (171), 103
(205)
Klazinga, A. H., 331 (58)
Klein, S., 247 (38)
Klingler, R. J., 5, 6 (22), 31, 43
(47),237,245,246(7),282 (28)
Klym, A., 100 (165)
Knifton, J. F., 355 (38)
Knifton, J. K., 354 (28b)
Knight, C. T. G., 84 (24)
Knighton, D. R., 181 (III), 182
(112)
Knipe, A. c., 312 (35)
Knizhnik, A. G., 366 (129), 367
(138)
Knowles, P. F .. 228, 229 (80)
Knowles, W., 365 (120)
Knowles, W. S., 354 (29)
Knox, S. A. R., 337 (87),341 (98),
343 (108)
Kobayashi, T, 355 (36), 363 (100)
Koch, H., 317 (50)
Kochetkova, A. P., 209 (126)
Kochi, J. K., 5, 6 (22),31,43 (47),
66 (78), 237, 245, 246 (6-7),
287 (28) (53), 359 (63)
Kodama, M., 132 (80)
Koenig, K., 365 (120)
Kohata, S., 203 (96)
Kohl, G., 353 (15)
Kojima, K., 224 (39)
Kok, R. A., 70 (109)
Kokkes, M., 120 (47a)
Kolthammer, BW. S., 239(1 1-12),
247 (38), 339 (91)
Kondo, S., 41, 46 (71)
Kondo, Y., 100 (164)
Konig, E., 194 (44)
Koningstein, J. A., 22 (88)
Konishi, H., 363 (100)
Konishi, S., 282 (29)
Konovalova, A. L., 106 (I)
Konstantatos, J., 64 (65), 274 (8),
317 (53)
Koppenol, W. H., 49 (110)
Koridze, A. A., 343 (105)
Koshelev, Yu. N., 361 (80)
Kostanski, M., 144 (25)
Kostic, N. M., 303 (7)
Koten, G. Y., 297 (89)
Kotzian, M., 320 (4)
Koval, C. A., 31, 45 (67)
Kovaleva, L. S., 363 (102)
Kozlov, Yu. N., 100 (166), 103
(204)
Kozlowska-Milner, E., 84 (28)
Kozuka, S., 82 (16)
Kraaijkamp, J. G., 19, 20 (71)
Kramer, G., 254 (61)
Kramer, H. E. A., 10 (42)
Krausz, E., 17 (66)
Kreiter, C. G., 320 (4), 326 (36),
374 (171)
I\..rentzien, H., 18,20 (69a), 151
(50)
Kresge, C. T., 291 (68)
Kress, J., 370 (153a), 371 (l53b)
Krischenbaum, L. J., 43 (51)
Krishnamoorthy, G., 227 (70)
431
Krishnamurthy, S. S., 94 (99)
Krishnamuthy, Y. Y., 62 (50)
Krishnan, C. Y., 48 (86), 54 (12)
Krishramurti, P. S., 71 (121)
Krist, K., 33, 47 (83)
Kristine, F. J., 73 (141), 36 (4)
Krochman, D. E., 61 (47)
Kroeger, M. K., 21 (79)
Kroger, P., 15 (107)
Kromer, L. U., 219 (II)
Krost, D. A., 252 (56)
Krusovsky, 361 (84)
Kryuchkov, S. Y., 189 (16)
Kubas, G. J., 268 (122)
Kucharska, M. M., 364 (112)
Kudaroski, R., 239 (12),248 (39),
320 (2)
Kulakov, Y. N., 360 (74)
Kumar, A., 65 (70), 226 (56)
Kumar, K., 5 (20), 29, 31, 33, 42
(40)
Kumobayashi, H., 369 (145)
Kump, R. L., 241 (23), 242 (25),
286 (51)
Kun, P. P., 313 (38)
Kundu, K., 297 (88)
Kung, W. -J., 204 (106)
Kunkely, H., 203 (99)
Kuokkanen, T., 87 (55)
Kupferschmidt, W. c., 25, 26, 36
(9), 155 (9)
Kurmoo, M., 22 (86-87)
Kursanov, D. N., 317 (52),364
(1I4a-b)
Kurvcsev, T., 215 (I)
Kustin, K., 68 (90),71 (112-113),
89 (64), 100 (160), 102 (196)
(198), 197 (59), 224 (37)
Kuszaj, J. M., 6 (24),30,32,42(43)
Kutal, c., 150 (46)
Kuvaev, B. E., 353 (15)
Kuyper, J., 112 (20)
Kuzina, A. F., 189 (16)
Kuznetsov, A. M., 4 (8), 6 (27)
Kwan, K. S., 191 (29),227 (75)
Kwiecinski, M., 364 (107)
Kynoheva, K. S., 159 (20)
Kyte, A. B., 87 (44)
Labinger, J. A., 331 (55)
Labuda, J., 139 (II)
Lacroce, S. J., 262 (97)
Lafont, D., 362 (95), 365 (123a)
Lagow, R. J., 284 (41)
Lagrange, J., 231 (94)
Lagrange, P., 231 (94)
Lahverta, P., 339 (91)
Lai, R. D., 128 (66)
Lai, T W., 368 (141)
Lai, Y. H., 358 (5Ib)
Laine, R. M., 351 (3), 364 (109)
Laird, J. L., 155 (6)
Lamanna, W., 333, 334 (69) (71)
Lambert, J. B., 83 (23)
Lampe, P. A., 226 (58)
432
Lamprecht, G. J., 173 (76)
Lan, B. Y., 84 (27)
Landvatter, E. F., 292 (69)
Langford, C. H., 174 (84)
Lapinte, c., 361 (88)
Lappert, M. F., 113 (26), 330 (54)
Lappin, A. G., 44 (60), 53, 54 (2),
56 (15), 199 (66), 231 (98)
Laranjeira, M. C. M., 53, 54 (2)
Larchner, J., 73 (135)
Lardicci, L., 368 (144)
Larkworthy, L. F., 133 (2)
Larroche, c., 372, 373 (165)
Larson, M., 209 (128)
Larsson, R., 374 (172)
Larsson, S., 6 (28)
Latif, L., 262 (99)
Lattes, A., 372, 373 (165)
Lau, T. c., 24 (8), 25 (7-8), 36 (8),
203 (97)
Lau, W., 287 (53)
Lauf, I. K., 192 (36)
Lauffer, R. B., 56 (21-22)
Laval, J. P., 372, 373 (165)
Lawrence, G. A., 89 (67), 153, 154
(3), 193, 194 (43)
Lay, P. A., 89 (67)
Lazzaroni, R., 356 (47)
Le Hoang, M. D., 282 (31)
Le Marechal, J. F., 363 (104)
Le Martret, 0., 314 (40)
Le Ny, J. P., 370 (I 53a)
Leconte, M., 372, 373 (165)
Ledezema-Sanchez, G., 16 (102)
Ledon, H. J., 360 (66)
Lee, B. I., 228 (77)
Lee, C. L., 375 (181)
Lee, J. B., 371 (156), 372,373 (167)
Lee, K., 330 (53)
Lee, R. A., 24, 36 (5)
Lee, Y. -N., 86 (40)
Lees, A. J., 241 (21)
Lefebvre, J., 15, 21 (80)
Leiberman, M. L., 178 (102)
Leidner, C. R., 38 (28)
Leigh, G. J., 358 (56), 371 (161),
376 (183)
Leipoldt, J. G., 148 (36), 173
(76-77)
Lemerle, J., 15, 21 (80)
Lemieux, R. U., 65 (75)
Lenenko, V. S., 366 (129)
Lentz, H., 158 (18)
Leopold, K., 47 (84)
Lerchner, J., 96 (128)
Lethbridge, J. W., 167 (54)
Letts, J. B., 332 (62)
Leupin, P., 29, 32, 44 (61)
Leussing, D. L., 64 (66-67)
Lever, A. B. P., 170 (67)
Levine, R. D., 4 (15), 10 (41)
Levisalles,IJ., 375 (179)
Lewis, E. J. R., 267 (110)
Lewis, J., 237 (3), 345 (114)
Lewis, N. A., 14, 15 (116), 41, 47
(80), 148 (37)
Lewis, T. J., 197 (57)
Lexa, D., 283 (39)
Li, T. T. -T., 42 (39)
Liangshiu, L., 192 (31)
Licht, E., 94 (100)
Liebhafsky, H. A., 97 (134)
Liesegang, G. W., 224 (34)
Lilie, J., 44 (59)
Lim, M. -c., 114 (32)
Lin, G., 356 (45a)
Lin, I. J. B., 332 (63)
Lin, S. -M., 292 (71)
Linck, R. G., 150 (45)
Lincoln, S. F., 132 (79), 177 (94),
215 (I), 216 (4-6),217(8),218
(4-6) (115), 219 (13), 221
(22-23) (25), 228 (79)
Lind, J., 100 (158)
Lindenberg, J., 16 (63)
Lindner, E., 94 (102)
Ling, S. S. M., 335 (76), 352 (10)
Lippard, S. J., 189 (15)
Lippmaa, E., 84 (25)
Lipscomb, W. N., 80 (4)
Lira, J. G. M., 192 (36)
Littlejohn, D., 90 (72), 227 (74)
Litvak, V. V., 313 (36-38)
Liu, G., 199 (73), 220 (16)
Liu, J. H., 62 (53)
Livage, J., 15,21 (80)
Lo, C. -F., 59 (31)
Loar, M. K., 296 (86)
Lock, C. J. L., 189 (12)
Logan, J., 7 (31), 9 (31) (95)
Long, J. R., 210 (135)
Longato, B., 363 (101)
Loots, M., 183 (118),276,277,278
(14)
Louw, W. J., 122(53-54), 124(57),
131 (54)(78), 290 (64-65), 291
(66-67), 322 (14)
Lown, J. W., 87 (50)
Loyola, V. M., 178 (102)
Lucherini, A., 289 (62)
Ludi, A., 17 (68), 18 (114)
Luft, G., 356 (41)
Luke, W. D., 328 (44)
Lum, V. R., 50, 51 (117)
Lunt, R. J., 315 (44)
Luong, J. c., 237, 246, 247 (5)
Mac B. Harrowfield, J., 175 (87)
MacDonald, J. J., 108 (10)
MacDougall, J. J., 322 (II)
Macartney, D. H., 191 (28) (30),
227, 228 (76)
Mack, K. B., 21 (73)
Macke, H., 150 (47), 174 (85), 209
(128)
Macneil, P. A., 366 (125)
Madan, S. K., 165, 166 (46), 206,
208 (114)
Author Index
Maeder, M., 171 (71)
Maestre, A., 71 (110), 10 I (169)
Maestri, M., 148 (38)
Magas, S., 144 (25)
Magde, D., 210 (129)
Magon, L., 190 (25-26)
Mahaffey, C. A. L., 333, 334 (70)
Mahajan, D., 365 (122)
Mahanti, M. K., 74 (149). 79 (3)
Mahapatro, S. N., 62 (53), 93 (92)
Mahmoud, F. M. S., 81 (10-11)
(13) (15)
Mahmoud, K. A., 241 (22)
Main, L., 84 (31)
Mainz, V. V., 254 (63)
Maitlis, P. M., 303 (8), 363 (99)
Malatesta, F., 106 (6)
Mal'chikov, G. D., 211 (142)
Malik, W. U., 37 (12)
Malin, J. M., 191 (29), 227 (75)
Malito, J., 255 (69)
Manganiello, F. J., 325 (32)
Mankin, J. c., 101 (181)
Manning, P., 345 (119)
Manojlovic-Muir, L., 341 (101)
Manotti-Lanfredi, A. -M., 121
(52),343 (107),345,346 (125)
Manov-Yuvenskii, V. I., 356 (42)
Manring, L. E., 95 (110)
Manrique, A., 353 (16)
Mansuy, D., 283 (38)
Mao, H. K., 64 (66)
Marangoni, G., 116 (36-39)
Marchal, D., 181 (110)
Marchi, A., 190 (26)
Marcus, R. A., 4 (10), 8 (33), 10
(40) (51), II (50) (52)
Marecek, J. F., 93 (95)
Mares, F., 360 (70)
Maresca, L., 117 (42)
Margerum, D. W., 31, 45 (67-69),
57 (2}-24), 58 (24)
59 (32),98 (149), 101
(173-174),224 (41-43),225
(42-43)
Margoliash, E., 49 (110)
Marinetti, A., 342 (102),346(126),
349 (102)
Markl, R., 240 (18), 303 (6)
Marko, L., 366 (131)
Markosyan, S. M., 364 (l14a-b)
Markovits, G. Y., 86 (41)
Markowitz, S. S., 88 (60)
Marks, T. J., 325 (25)
Marquet-Ellis, H., 363 (104)
Marsella, J. A., 283 (34), 337 (88),
356 (48)
Marshall, L. E., 73 (136)
Marshall, P. A., 221 (25)
Martell, A. E., 170 (66)
Martin, J. c., 82 (17)
Martin, V. S., 360 (70)
Martinelli, F., 366 (134)
Martinengo, S., 344 (112)
Author Index
Martinsen, 1., 16 (105)
Marty, W., 161 (31) (35),162 (35)
Maruthamuthu, P., 98 (146)
Marzilli, L. G., 181 (107)
Mascharak, P. K., 16(103),19,21
(74)
Mashima, K., 330 (53)
Mashima, M., 93 (90)
Masloch, B., 97 (136)
Mason, 1., 84 (26)
Masuda, A., 354 (33)
Masui, T., 232 (101)
Mategi, K., 197 (58)
Mathey, F., 108 (10), 322 (II)
r"athieu, R., 358 (56)
Mathur, M. A., 93 (87)
Mathur, P. N., 227 (63), 348 (130)
Matin, R., 346 (126)
Matisons, 1. G., 253 (59)
Matsubara, T., 15(107),33,48(87)
Matsuda, A., 354 (3Ia)
Matsumoto, A., 72 (129), 170 (69)
Matsumoto, S., 114, 115, 119 (33)
Matsumoto, Y., 145 (30),151 (51)
Matsumura, E., 364 (Ilia-b)
Matsuura, N., 96 (114), 197 (58)
Matsuura, T., 72 (132)
Matteoli, U., 351 (6)
Mattson, B. M" 249 (47)
Matusinovic, T., 34, 48 (99)
Matveev, K. I., 361 (84)
Mauermann, H., 238 (8), 359 (59)
Mauk, A. G., 50, 51 (112)
Maverick, A. W., 49 (102-103),
352 (7)
Mawby, R. 1., 250 (50),305 (15)
Maya, L., 92, 93 (83)
Mazanec, T. 1., 332 (62)
Mazzi, U., 190 (25-26), 321 (9)
Mazzocchin, G. A., 321 (9)
McAlister, D. R., 356 (45c)
McArdle, 1. Y., 230 (90)
McArdle, P., 318 (55) (56)
McAteer, C H., 209 (125), 251
(54), 333, 334 (73)
McAuley, A., 31, 43 (50), 44 (58),
191 (28) (30), 199 (66),211
(141),227,228 (76),231 (98)
McAuliffe, C A., 360 (72)
McCarthy, C A., 97 (131)
McCarthy, T. J., 124, 125 (59a),
299 (93-95)
McCormick, F. B., 302 (5), 325,
326 (30)
McCullen, S. B., 255 (68)
McDonald, W. S., 305 (14)
McElligott, P. J., 305 (13)
McGarrity, J. F., 352 (8)
McGlinchey, M. J., 342 (102),346
(126), 349 (102)
McGuiggan, M. F., 354 (32)
McGuiness, S. 1., 312 (35)
McHatton, R. C, 66 (81), 200
(75), 281 (23)
McKee, M. L., 80 (4)
McKee, Y., 9 (97)
McKenna, P., 336 (80)
McKinney, R. 1., 294 (79), 371
(156)
McLendon, G., 48 (96), 49 (III),
170 (66)
McLendon, Gr., 33, 47 (82)
McMahon, I. J., 333, 334 (72)
McMillin, D. R., 45 (66)
McNulty, G. A., 345 (120)
McPartlin, M., 345 (119)
McWhinnie, W. R., 99 (154)
Mead, K. A., 341 (98)
Mealli, C, 329 (48)
Meckstroth, W. K., 255 (65)
Medina, J. D., 226 (52)
Meek, D. W., 332 (62), 362 (97)
Mehrotra, R. N., 63 (54) (58), 64
(68-69)
Mehta, M., 63 (58), 64 (68-69)
Mekhtiev, S. D., 360 (74)
Melo, F., 353 (16)
Menicagli, R., 368 (144)
Mentasti, E., 56 (16), 113 (28-29),
114 (30b), 220 (18),226
(54-55) (59) (61), 227 (65) (68)
Mentzen, B., 346 (126)
Merbach, A. E., 199 (74),217 (9),
220 (15) (17), 221 (24)
Mercer, W. C, 256 (79)
Merenyi, G., 100 (158)
Merrill, R. E., 351 (6)
Merritt, E. A., 177 (91-93)
Mersh, F. D., 333 (68)
Mertes, K. B., 21 (77)
Mestroni, G., 366 (127) (134),367
(135)
Mesubi, M. A., 323 (17)
Meuldijk, J., 108 (9), 109 (14)
Meyer, F. K., 220(17)
Meyer, T. A., 87 (49)
Meyer, T. 1.,14(109),15(113),16
(57-58),32 (74), 39 (31), 46
(73), 74 (147), 94 (101),201
(83), 202 (94), 204 (94) (107),
324 (21), 360 (73)
Meyerstein, D" 38 (30), 43 (51),44
(62),69 (100), 97 (142),133 (5)
Michalksi, 1., 95 (104)
Michelon, G., 116 (36-39)
Midollini, S., 329 (48),332 (61)
Mikhail, F. M., 194 (47)
Milazzani, Q. A., 27, 37 (15)
Miles, W. H., 340, 341 (97)
Miller, D. S., 48 (96)
Miller, L. P., 134, 136, 138 (9),249
(45)
Mills, R. M., 345 (116) (123)
Milone, L., 345 (115) (125), 346
(125),348 (128)
Milstein, D., 293 (74)
Mimoun, H., 359 (64)
Minato, T., 5 (23), 56 (18)
433
Minatu, T., 56 (17)
Mingos, D. M. P., 130 (74),315
(42)
Miralles, A. 1., 14( 108),38,40(29)
Mirbach, M. F., 352 (l4a)
Mirbach, M. 1., 352 (l4a)
Mirti, P., 230 (86)
Mishra, S. K., 68(92-93), 70(106),
95 (106-107)
Mislow, K., 348 (127)
Mispelter, 1., 283 (39)
Misra, S. A., 71 (III)
Mitani, H, 364 (33)
Mitchell, P. R., 171 (71)
Mitchell, T. R. B., 361 (83)
Mitta, A. E. A., 190 (24)
Mittal, A., 101 (187)
Mittal, P. K., 332 (66)
Miyake, S. -I., 31, 46 (72)
Miyamoto, T., 119 (44)
Miyashita, A., 369 (145),370 (150)
Miyoshi, K., 151 (51)
Mizuno, K., 362 (90)
Mlodnicka, T., 360 (75a)
Mocak,l., 139 (II)
Mochida. I., 364 (Ilia-b), 375
(177)
Modelli, A., 250 (52)
Modena, G., 360 (67-69)
Moffatt, 1. R., 91 (79)
Mohapatra, B. K., 114, 119 (34)
Mohapatra, S. K., 157 (13)
Moiseev, I. I., 363 (103), 367 (138)
Mol, 1. C, 372 (164)
Molle, G., 285 (45)
Monacelli, F., 155 (8), 197 (61),
231 (95)
Mondal, 1. U., 289 (59)
Moneti, 1., 329 (48)
Monig, J., 87 (54)
Monnerat, A., 217 (9)
Monnerat, A. R., 220 (17)
Monshi, M., 310 (29)
L., 139 (12)
0., 139 (12), 212 (144)
Montrasi, G., 353 (l7a-c)
Moodie, R. B., 84 (29) (31)
Moody, D. C, 268 (112)
Mooiman, M. B., 288 (58)
Mooney, W. F., 33, 47 (82)
Moore, C 1., 9 (96)
Moore, E. 1., 265 (107)
Moore, P., 61 (41), 133 (I), 209
(125), 217 (9), 226 (58), 251
(54), 333, 334 (73)
Moore, S. S., 297 (90), 371 (157)
Moorima, M. B., 74 (150)
Moran, G., 318 (56)
Morando, P. 1., 59 (28)
Morarskiy, A., 296 (85)
Mordenti, L., 314 (40)
Morgan, T. D. B., 92, 93 (84)
Morliere, P., 43 (52-53), 44
(53-54),97 (137)
434
Moroi, H., 152 (62), 227 (72)
Morokuma, K., 293 (76)
Morris, D. E., 352 (12)
Morris, G. E., 209 (125), 251 (54),
333, 334 (73)
Morris, P. J., 181 (109)
Morrison. M. M., 56(19), 96(113)
Mortreux, A., 353 (19a), 372
(163)
Morvillo, A., 294 (80-81)
Motegi, K., 96 (114)
Motell, E., 342 (104)
Motsch, A, 240 (19)
Mouchel, B., 205 (III)
Moxon, N. T., 72 (125)
Moyer, B. A., 32 (74), 46 (73), 74
(147), 94 (101), 360 (73)
Muetterties, E. L., 251 (55), 315
(43), 324 (23), 331 (57), 358
(53a-b), 363 (105a-b)
Muhlemeier, J., 240 (18), 303 (6)
Muir, K. W., 341 (101)
Muir, M. M., 158 (17)
Muller, H., 248 (40)
Mulzzani, Q. G., 48 (88-89)
Mund, S. L., 363 (103), 367 (138)
Munro, G. A. M., 333, 334 (70)
Murati, I., 232 (102)
Murray, H. H., 328 (42)
Murray, M., 345 (117)
Murray, R. W., 38 (28)
Murray, S. G., 106 (3)
Murrer, B. A., 362 (95)
Murthy, C. P., 65 (72)
Mushenko, D. Y., 361 (80)
Muth, H., 232 (104)
Mutin, R., 344 (III)
Mutin, R., 362 (96)
Muzart, J., 367 (137)
Mysov, E. I., 366 (129)
Nadjo, L., 366 (133)
Nagasawa, A., 224 (36)
Nagasuna, K., 330 (53)
Nagel, C. c., 343 (109), 359 (61)
Nagori, R. R., 63 (58), 64 (68-69)
Nagy, L., 73 (138), 96 (122-123)
Nagypal, I., 230 (81-82) (84':'85)
Nair, P. K. R., 101 (187)
Naito, S., 90 (73)
Nakajuma, M., 95 (III)
Nakamura, A, 330 (53)
Nakamura, Y., 114 (34-35), 115
(35), 119 (34-35) (44), 125,
127, 128 (61), 295 (84), 322
(13)
Nakano, K., 152 (62),227 (71-72)
Nakashima, M., 174 (82)
Namiki, A., 10 (44)
Nanda, R., 157 (14)
Nanda, R. K., 166 (50)
Nanni, E. J., 96 (113) (115-117)
Nappa, M. J., 286 (52)
Narayanaswamy, R., 241 (22)
Narusawa, Y., 152 (62), 227
(71-72)
Natarajan, P., 33, 47 (81), 66 (79)
Natile, G., 117 (42), 121 (52)
Naumann, F., 238, 239 (9)
Navaratnam, S., 97 (133)
N azimok, F. Y., 360 (74)
Nefedov, B. K., 356 (42)
Nejem, L., 15,21 (80)
Nelsen, S. F., 93 (86)
Nelson, J. H., 108 (10), 119 (45),
177 (99), 182 (117), 322 (II)
(16)
Neogi, G., 60 (34-35),98 (147)
Nesbit, M. C., 72 (124)
Neta, P., 3 (2), 44 (55-56), 55 (7),
66 (77), 283 (37)
Netzel, T L., 13 (56), 15 (56)
(107), 39, 41 (34)
Newman, K. E., 217 (9),220 (17)
Newman, L., 86 (41)
Newton, M. D., 4 (9),7 (31-32), 9
(31) (95)
Ng, F. T. T., 277 (16)
Nicholas, K., 262 (98)
Nicholson, B. K., 253 (59)
Nicholson, P. N., 362 (95)
Niedernhofer, B., 232 (104)
Niewahner, J., 362 (97)
Nigan, P. c., 64 (62)
Nilsson, N., 230 (88)
Nishida, Y., 96 (124)
Nishigawa, K., 72 (132)
Nishikawa, S., 93 (90)
Nishimoto, K., 160 (25)
Nishinaga, A., 72 (132)
Nishizawa, M., 173 (78)
Nist, K., 326 (36)
Nix, G. Jun., 366 (126)
Nocera, D. G., 49 (104)
Nolan, K. B., 164 (44)
Nord, G., 57, 58 (25),101 (175),
196 (54),212 (144)
Nordberg, R. E., 361 (81)
Nordmeyer, F. R., 162 (36)
Norman, P. R., 155(10), 163(38)
(40), 176 (90)
Norris, W. P., 178 (101)
Norton, J. R., 257 (83), 348 (127)
Noth, H., 80 (5-6)
Nour, E. M., 22 (85)
Novakov, T, 88 (60)
Novikov, Y. T, 227 (67)
Novikova, E. S., 374 (173)
Novikova, N. M., 227 (67)
N owogrocki, G., 20 I (82)
Noyes, R. M., 71 (116-118), 96
(130), 101 (185), 102
(192-194)
Noyori, R., 369 (145) (147)
Nutkovich, M., 38 (30)
Nulton, A., 303 (8)
Nuzzo, R. G., 124, 125 (59a), 299
(93-95)
Author Index
Obara, S., 293 (76)
Oblath, S. B., 88 (60)
O'Brien, P., 148 (35), 233 (III)
O'Connell, C. M., 202 (91)
Oda, Y., 369 (147)
Odiaka, T., 306, 307 (18-20)
Ogata, I., 353 (18), 354 (23)
Ogata, Y., 74 (145),96 (129), 100
(164)
Ogilby, P. R., 95 (109)
Ogino, H., 26, 37 (13), 143 (21),
249 (44), 274, 275 (7)
Ogino, K., 163 (41)
Ogita, M., 114, 119 (34)
Oh, S. -0., 158 (18)
O'Hare, P. A. G., 99 (156)
Ohashi, Y., 211 (140)
Ohgo, Y., 365 (119)
Ohyoshi, A, 203 (96)
Oikawa, H., 63 (60)
Oishi, N., 96 (124)
Ojima, I., 353 (20)
Ojo, J. F., 32, 46 (75-76)
Ojodium, A. 0., 32, 46 (75)
Okamoto, H., 375 (177)
Okano, T., 359 (62), 363 (100)
Okazaki, H., 184, 185 (120)
Okeya, S., 114 (34-35), 115 (35),
119 (34-35) (44)
Okolow-Zubkowska, M., 67 (86),
91 (80a)
Okrasinski, S. J., 365 (124)
Oku, K., 354 (33)
Okubo, T., 159 (19)
Olabe, J. A., 191 (27)
Olarte, B., 151 (50)
Olive, S., 358 (5Ia), 373 (168)
Olsen, D. J., 330 (51)
Olsen, R. J., 254, 255 (64)
Olsson, L. F., 57, 58 (26), 10 I
(172), 128 (68)
Olsson, T., 84 (30)
Olubuyide, 0., 24 (6),32 (75-76),
36 (6), 46 (75-76)
Omori, T, 190 (19)
Ondrechen, M. J., 6, 13 (26)
Onuki, Y., 114, 119 (34)
Ooi, S., 72(132), 87(47),119(44)
Orban, M., 71 (120), 100 (160),
101 (190), 102 (190)
(200-201), 103 (202)
O'Rear, S. P., 252 (56)
Orengo, c., 73 (137)
Orlandi, G., 10 (45)
Orlandini, A, 332 (6I)
Oro, L., 353 (16)
Orpen, A G., 340 (96), 343 (108),
345 (117)
Orrell, K. G., 213 (148-150), 332
(66),337 (81-86),341 (100)
Ortaggi, G., 144 (23), 155 (8)
Orvig, c., 189 (II)
Osborn, J. A, 370 (153a), 371
(I 53b)
Author Index
Osella, D., 343 (106), 345 (115)
(125), 346 (125)
348 (128-129)
Osheroff, N., 49 (110)
Otsuka, S., 359 (62), 369 (145)
Ott, K. C, 372, 373 (167)
Otto, M., 73 (135),96 (128)
Outram, J. R., 87 (46)
Overbeck, 0., 297 (89)
Owens, G. D., 31, 45 (68)
Owens, K., 284 (42)
Oyama, N., 38 (27)
Ozawa, F., 125, 127, 128 (61),295
(84), 322 (13)
Ozkar, S., 320 (4)
Pace, L. J., 16 (105)
Pacheco, A. D., 226 (52)
Packer, J. E., 87 (54)
Pada, R. K., 60 (34-35)
Pagani, G., 353 (l7a-c)
Page, J. A., 284 (40)
Pagsberg, P., 57, 58 (25), 10 I (175),
196 (54)
Paik, C H., 189 (10)
Pain, G. N., 345 (114) (116)
Paladini, L., 355 (39)
Palazzotto, M. C, 199 (69)
Palmer, D. A., 106(5), 153(2),154
(5), 207 (118) (120), 208 (118)
(121), 230 (87)
Palmer, M. R., 67 (85)
Panda, A. K., 93 (91-92)
Panda, M., 204 (102)
Panda, R. K., 98 (147)
Pandurengan, T., 98 (146)
Panigrahi, G. P., 93 (91-92)
Pankowski, M., 283 (36)
Paolucci, G., 116 (36)
Pap, T., 73 (135), 96 (128)
Papadopoulos, P., 87 (51-52)
Papaefthymiou, G. C, 19, 2 I (74)
Papson, G. A., 102 (197)
Paradisi, c., 170 (65)
Paras had, R., 203 (95)
Pardy, R. B. A, 326 (37),333 (68),
374 (175)
Parenago, O. P., 363 (102)
Parera, Y. E., 190 (24)
Parigi, K. J., 100 (162)
Parish, D. R., 366 (126)
Parish, P. Y., 3 I 5 (44)
Parker, D., 362 (95), 364(1 16), 365
(121)
Parnes, Z. N., 364 (l14a-b)
Parsons, B. J., 97 (133)
Patai, S., 177 (96)
Patel, G., 129 (69)
Patel, R. c., 221 (21)
Pati, S. c., 204 (102)
Patterson, H. H., 16(110-1 I I), 43
(52-53),44 (53-54),97 (137)
Pauson, P. L., 333, 334 (70)
Pavlovic, D., 232 (102)
Paxson, T. E., 358 (52b)
Peacock, R. D., 188 (6-7),206
(112)
Pearsall, K. A., 67 (87-88),89 (65),
90 (65) (71)
Pearson, A. J., 3 10 (27)
Pearson, R. G., 238 (8), 291 (68),
359 (59)
Pecht, L., 51 (I 18)
Pedersen, B., 57, 58 (25), 10 I (175),
196 (54)
Peguy, A, 218 (114)
Peiffer, G., 368 (140)
Pelizzetti, E., 29 (36), 38 (23), 39
(36),48 (97), 56(16), 114(30b)
Peloso, A., 209 (127)
Pennesi, G., 197 (61), 231 (95)
Pennington, D. E., 26, 36 (11),145,
148 (29)
Penton, J. R., 87 (53)
Perkins, I., 375 (180)
Perlman, M. L., 9 (36)
Perlmutter-Hayman, B., 227 (64)
Perrior, T. R., 310 (27)
Pete, J. P., 367 (137)
Peters, G., 190 (18)
Petersen, J. D., 192 (31), 203 (98),
210 (98) (132), 211 (98)
Peterson, B. S., 257, 258 (81)
Peterson, J., 73 (137)
Petit, E, 353 (l9a), 368 (140),372
(163)
Petit, M., 372 (163)
Petrou, A., 274 (8), 317 (53)
Petrovskii, P. Y., 343 (105)
Petrucci, S., 223 (32)
Pfenning, K. J., 192 (31)
Pfister-GuilIouzo, G., 318 (54)
Pfliiger, F., 295 (82)
Phelan, K. G., 87 (56),88 (58) (61)
Phillips, I. G., 129 (70)
Phillips, T. E., 16 (105)
Phu, T. N., 352 (l4a)
Piazzesi, AM., 354 (25)
Pickering, R. A., 302 (4)
Pickett, C. J., 376 (183)
Pidock, A., 297 (88)
Pierce, R., 356 (45b)
Pierloot, K., 193 (42)
Pierpont, C. G., 256 (79)
]lignolet, L. H., 199 (69), 354 (32)
Pina, F. J. S., 249 (43)
Pino, P., 354 (27)
Pisaniello, D. L., 215 (1),217 (8),
219 (13), 221 (22-24)
Pittman, C U. Jr., 354 (28a)
Pizer, R. D., 177 (95)
Pladziewicz, J. R., 29, 42 (38)
Plotkin, J. S., 345 (118)
Po, H. N., 59 (31), 74 (148)
Poe, A., 254 (61-62), 255 (69-70)
(73), 256 (76), 257 (80)
Poggi, A., 44 (57)
Polm, L. H., 339 (92)
Poltowicz, J., 360 (75a)
Pomerantz, M., 360 (69)
Pool, K., 29, 39 (37)
435
Poon, C. -K., 24 (8), 25, 36 (7-8),
155 (10), 203 (97)
Pope, M. T., 15,22 (81)
Posey, F. A., 92, 93 (83)
Posin, B., 286 (50)
Powell, D. B., 22 (82), 58 (27b),
210 (134)
Powell, M. c., 167 (55)
Powell, R. E., 90 (74)
Poznyak, A. L., 151, 152 (52-53)
Prabhananda, B. S., 227 (70)
Pramauro, F., 38 (23)
Prasad, D. R., 147 (32)
Prasad, R. K., 63 (59)
Prasad, S., 63 (59)
Pratt, J. M., 74 (150),288 (58)
Precigoux, G., 314 (40)
Preece, M., 361 (79)
Preetz, W., 190(18),205(108-110)
Pregosin, P. S., 120 (48)
Prince, R. H., 194 (45)
Pring, G. M., 213 (149-150), 341
(100)
Pringle, P. G., 332 (64)
Prodolliet, J., 352 (8)
Prow, W. F., 5 (18)
Pucci, S., 356 (47)
Puddephatt, R. J., 113 (25), 131
(77), 252 (57), 298 (92), 299
(92) (97),335 (76),341 (101),
352 (10)
Puebla, P., 339 (91)
Pujari, M. P., 73 (140), 96 (125), 97
(141)
Purcell, W. L., 175 (88), 178 (100)
Purmal, A. P., 100(166), 103(204)
Puzic, 0., 86 (39)
Pyszczek, M. F., 362 (89)
Que, L., 56 (21-22), 199 (69)
Queir6s, M. A. M., 332 (65)
Quick, G. R., 61 (41), 226 (58)
Quicksall, C. 0., 17 (67), 46 (78)
Quignard, F., 372, 373 (165)
Quinn, S., 263 (102)
Rabai, G., 91 (80b)
Rabie, D. R., 148 (36), 173 (76)
Radcliffe, M. D., 325 (32)
Radhakrishnamurti, P. S., 71
(Ill)
Radlowski, C. A., 24 (100),25
(100-10 I), 26 (100), 27
(100-101),33 (101), 34(100),
35 (100-101), 48 (100-101),
62 (50-51)
Raghavan, N. Y., 66 (79),101 (168)
Raghu, S., 262 (98)
Rahman, M. T., 371 (161)
Rahil, J., 94 (97)
Raimondi, L., 353 (l7b)
436
Rajagopal, S" 60 (37)
Raju, J, R., 37 (20)
Ramachadraiah, G., 72 (130)
Ramamurthy, S., 280 (21)
Raman, S., 192 (33-34)
Ramasami, T., 147 (32)
Ramaswamy, D., 60 (34-35), 98
(147), 147 (32)
Ramesh, S., 62 (53)
RaI)lirez, F., 93 (95)
Ramsden, J., 48 (98)
Ramsden, J. H., 169 (63)
Rao, B. S., 157 (14)
Rao, M. A., 61 (45)
Rao, P. J. P., 65 (71)
Rao, T. N., 61 (45), 63 (61), 65
(71-72)
Rao, V. H., 60 (38-39),68 (91),89
(63), 99 (152-153)
Rappe, A. K., 371 (159)
Rasmussen, R S., 210 (136)
Raston, C. L., 330 (54)
Ratner, M. A., 4 (15), 16 (63)
Rauchtuss, T. R, 292 (69)
Rauscher, W., 10 (42)
Raverty, W. D., 311 (31)
Ray, N., 166 (50)
Raycheba, J. M. T., 57 (23-24), 58
(24), 101 (173-174), 224, 225
(43)
Raymond, K. N., 199 (71)
Razay, H., 338 (90)
Read, G., 361 (78)
Read, R. A., 224 (41)
Reagor, B. T., 29, 42 (41)
Reba, R. c., 189 (10)
Rebenstorf, B., 374 (172)
Reckley, J. S., 64 (63), 103 (203)
Reddy, A. S., 69 (99)
Reddy, R S. R., 371 (160)
Reddy, J. N., 69 (99)
Reddy, K. R, 63 (61), 65 (72)
Redi, M., 6 (25)
Reed, C. A., 9 (97)
Reed, J. L., 174 (83)
Reed, J. W., 62 (50)
Reed, N. V., 69 (96), 195 (50)
Reenstra, W. W., 280 (22)
Rees, D. c., 310 (27)
Reeves, P. c., 311 (30), 316 (48)
Reger, D. L., 305 (13)
Reglinski, J., 192 (32)
Rehder, D., 238, 239 (9), 321 (8),
345 (113)
Rehm, D., 10 (39)
Rehorek, D., 79 (I)
Reich, K. A., 71 (136)
Reichenbach, G., 287 (54)
Reid, L. S., 50, 51 (112)
Reiffer, U., 232 (106)
Reilly, C. A., 358 (52b)
Reinsborough, V. c., 225 (45-46)
Reinten, M., 19, 20 (71)
Remington, S., 366 (126)
Rempel, G. L., 277 (16)
Renkema, W. E., 163 (39)
Reshef, D., 366 (132)
Rest, A. J., 241 (22)
Reynolds, G. D., 182 (112)
Reynolds, W. L., 168 (60)
Rheingold, A. L., 325 (31)
Ribas, J., 152 (60)
Riccieri, P., 139 (13),141,146(15),
150 (43)
Rice, C. W., 127 (62)
Ricevuto. V., 114 (31), 128 (64),
233 (110)
Richards, R. L., 67 (83)
Richardson, R. J., 97 (132)
Richens, D. T., 31, 45 (70)
Richman, R. M., 21 (79)
Richmond, T. G., 243, 244 (31),
255 (71),262 (94-95)
Ridd, J. H., 85 (32-37), 86 (38)
Ridd, M. J., 61 (40), 201 (84)
Riddell, F. G., 212 (147), 336 (79)
Riddles, P. W., 161 (33)
Rieger, P. H., 95 (108), 233 (113),
237, 252 (4), 253 (59)
Riley, G. E., 298, 299 (92)
Rillema, D. P., 21 (73)
Rindermann, W., 157 (12)
Rinzel, J., 101 (182)
Risley, J. M., 89 (62)
Rispoli, P. L., 114 (30a)
Ritchie, C. D., 302 (3)
Ritter, G., 194 (44)
Riviere, H., 361 (88)
Rizkella, E. N., 73 (139), 96 (127)
Robbins, G. L., 37 (16)
Roberts, D. A., 256 (79)
Roberts, J. D., 91 (78)
Roberts, N. K., 121 (51), 364(117),
365 (124), 366 (125)
Robertson, G. R, 263 (104)
Robin, M. R, 17 (65)
Robin, Y., 282 (31)
Robinson, B. H., 254 (60)
Robinson, S. D., 332 (65)
Robinson, S. R., 85 (33)
Robson, K., 329 (47)
Rocek, J., 62 (53)
Rodehorst, R. M., 290 (63)
Rodenas, E., 91 (79)
Roe, G. M., 97 (134)
Roessling, G., 158 (18)
Roettger, L. J., 100 (162)
Rofer-DePoorter, C. K., 356 (43)
Rogers, J. H., 206 (112)
Rogers, W. N., 284 (40)
Rogic, M. M., 361 (85a)
Rokicki, A., 358 (57).
Rollick, R. L., 66 (78)
Roman, E., 315 (45),317 (51)
Romeo, R., 109(15), 117(40-41)
Roncari, E., 190 (25-26),321 (9)
Roobeek, C. F., 374 (176)
Roof, M. J., 59 (30)
Author Index
Rooney, J. J., 361 (83), 371 (160),
372 (164)
Roose, W., 321 (8)
Root, K. S., 285 (44)
Root, L. J., 6, 13 (26)
Root, M. J., 147 (34)
Rooze, H., 100 (159)
Roper, W. R., 262 (96)
Rosan, A. M., 327 (40)
Rose, E., 314 (40-41), 315 (41),
318 (54)
Rose, F., 375 (179)
Rose-Munch, F., 265 (107), 375
(179)
Rosenberg, E., 343 (107), 345
(115), 348 (128)
Rosenblum, M., 262 (98), 304
(10-11), 329 (50)
Rosolovskii, V. Ya., 89 (68)
Rosseinsky, D. R., 21 (78)
Rossi, A., 362 (91)
Rossi, A. R., 371 (156)
Rossi, G., 197 (61),231 (95)
Rossi, R., 190 (25-26)
Roth, G. P., 366 (126)
Rothrock, R. K., 265 (107)
Rothwell, I. P., 345, 347 (122)
Rottler, R., 374 (171)
Roulet, R., 120 (46),322,323 (12)
Rowan, N. S., 185 (122)
Rowan, R., 185 (122)
Rowland, K. A., 130 (74)
Royo, M., 353 (16)
Rubini, P., 218 (114)
Rudenko, A. P., 91 (81)
Rudler, H., 375 (179)
Rudler, M., 375 (179)
RufiI1ska, A., 327 (39)
R umfeldt, R. c., 209 (128)
Runge, T. A., 369 (149)
Rupprecht, G. A., 374 (l70a)
Russel, G. A., 284 (42)
Russell, D. R., 188 (7), 336 (80)
Rutt, K. J., 371 (158)
Ryan, D. A., 66 (80),71 (123), 75
(151), 133 (4), 134, 135 (7),
249 (46), 272 (4), 274 (9)
Ryan, R. R., 268 (112)
Rybak, W., 13, 15 (56), 39, 41 (34)
Rybak, W. K., 366 (128)
Rybka, J. S., 31, 45 (69)
Saaman, A. A., 19, 20 (71)
Saar, D., 225 (51)
Sabbatini, N., 10 (45-46)
Saburi, M., 63 (60)
Sacconi, L., 329 (48)
Sachinidis, J., 226 (60)
Sachtler, W. M. H., 359 (65)
Sackett, J. A., 241 (23), 286 (51)
Sacki, T., 96 (114)
Sadler, P. J., 110 (16)
Saeki, T., 197 (58)
Saha, N. c., 44 (56)
Author Index
Sahami, S., 4 (14)
Sailers, E. L., 358 (58)
Saillard, J. -Y., 342 (102), 346
(126), 349 (102)
Saito, K.,4I,46(71), 72(129),170
(69), 188 (I)
Saito, 0., 295 (83)
Saji, T., 21 (76)
Sakabe, Y., 145 (30)
Sakaguchi, U., 184, 185 (120)
Sakai, M., 368 (143)
Sakakibara, Y., 368 (143)
Sakanoue, S., 10 I (180)
Sakurai, H., 59 (29)
Salazar, T., 73 (134)
Saliby, M. J., 165 (46), 206, 208
(114)
Salyn', Ya V., 203 (101)
Salzer, A., 341 (99)
Samsonov, A., 84 (25)
Samuel, E., 283 (36)
Samuels, Gr. J., 32 (74)
Samuels, S. B., 304 (II)
Sanchez, c., 15, 21 (80)
Sanchez-Delgado, R. A., 364 (113)
Sancho, J., 371 (l62a-b)
Sandall, J. P. B., 85 (35-37)
Sanders, J. K. M., 333 (68)
Sangster, D. F., 62 (52), 97 (139)
Santappa, M., 147 (32)
Santi, R., 286 (52)
Sapne, N. Y., 73 (133)
Saprykova, Z. A., 230 (83)
Sarange, L. D., 71 (121)
Sarawek, K., 58 (27b), 210 (134)
Sargeson, A. M., 62 (52), 89 (67),
97 (139), 155 (7), 161 (29-31),
164 (43), 175 (87), 177 (95),
179 (105),181 (107-108)
Sarhan, J. K. K., 305 (12)
Sarry, B., 324 (22)
Sasaki, Y., 41, 46 (71), 72 (129),
170 (69), 198 (65)
Sasseville, R. L. P., 174 (84)
Satchell, D. P. N., 129 (69)
Sattar, S., 219 (10)
Sattelberger, A. P., 340 (94)
Satterthwait, A. C., 93 (94)
Saus, A., 352 (l4a)
Saveant, J. -M., 283 (39)
Sawyer, D. T., 56 (19-20), 96(113)
(115-117)
Sayer, B. G., 342 (102), 346 (126),
349 (102)
Sazaki, H., 114, 119 (34)
Sbiti, N., 225 (48)
Sbrana, G., 355 (39)
Sbriziolo, c., 63 (56-57), 227 (66)
Scagnolari, F., 250 (52)
Scaiano, J. C., 80 (7)
Scandola, F., 5 (21), 10 (45)
Scandola, M. A. R., 173 (81)
Scardellato, c., 360 (67)
Schaefer, H. F. III, 326 (33)
Schaefer, W. P., 371 (156)
Schafer, K., 95 (105)
Schaffernicht, R., 324 (22)
Schatz, P. N., 16, 17 (62), 22
(90-91)
Schenk, W., 248 (39-40), 320 (2)
Schenkluhn, H., 351 (4)
Scherer, O. J., 124 (58)
Schiavon, G., 170 (65)
Schichman, S. A., 50, 51 (113)
Schiraldi, D. A., 300 (98)
Schmeil, R. H'., 16 (57)
Schmidt, R., 106 (5),149, 150(42),
173 (79), 230 (87)
Schmidt, R. E., 257, 258 (81)
Schmidt, S. P., 255 (75)
Schmitz, G., 100 (159)
Schmitz, J. E. J., 19,20 (71), 112
(23)
Schmonsees, W. A., 30, 32, 42 (43)
Schmonsees, W. G., 6 (24)
Schneider, H., 222 (26-28), 223
(29-31), 224 (35), 226 (57)
Schneider, I., 222 (28)
Schofield, K., 84 (29) (31)
Schrauzer, G. H., 182 (115)
Schrauzer, G. N., 67 (85), 279
(17-18)
Schrock, R. R., 335 (74-75), 352
(9),371 (l62a-b), 374
(l70a-b)
Schrod, M., 356 (41)
Schroeder, L., 353 (15)
Schroth, G., 327 (39), 330 (52)
Schuchman, M. N., 97 (135)
Schumann, M., 232 (103) (106)
Schunn, R. A., 358 (53b)
Schuster, G. B., 5 (21)
Schwab, A. P., 117 (40-41)
Schwager, I., 354 (28b)
Schwartz, G., 286 (50)
Schwartz, J., 286 (49)
Schwartz, S. E., 86 (40-41)
Schwarz, H. A., 55 (8)
Schwarz, W., 87 (55)
Scott, J. W., 366 (126)
Scotton, M. J., 247 (35)
Scotton, M. S., 283 (35)
Scrimin, P., 360 (67)
Scrinivasan, S., 60 (37)
Secco, F., 220 (18), 227 (65)
Seconi, G., 81 (12)
Seddon, K. R., 201 (86)
Sedney, D., 18 (114)
Seeber, R., 130 (73), 321 (9)
Sehested, K., 96 (118-119), 101
(171), 103 (205)
Seitz, G., 41, 47 (80)
Seki, H., 163 (41)
Selivanova, G. A., 313 (36)
Sellars, P. J., 185 (121)
Sellers, R. M., 3 (4)
Sen Gupta, K. K., 65 (73)
Seno, M., 101 (184)
437
Sequera, B., 226 (52)
Serpone, N., 27, 37 (15),148 (38),
149 (41), 151 (48),211 (137),
324 (20)
Sethuran, B., 61 (45), 63 (61), 65
(71-72)
Setkina, V. N., 317 (52)
Sevcik, P., 101 (186)
Sexton, D. A., 210 (129)
Sham, T. K., 9 (36-37)
Shapley, J. R., 258 (86)
Sharma, K. R., 364 (110)
Sharma, R. G., 69 (98)
Sharpless, K. B., 360 (70)
Shaver, A., 128 (66), 263 (102)
Shaw, A. C., 338 (89)
Shaw, B. L., 130 (75), 289 (61),
305 (14), 332 (64)
Sheldon, R. A., 359 (63) (65)
Shepherd, R. E., 36 (4), 73 (141)
Sheridan, P. S., 206, 208 (114)
Sherry, L. J. S., 336 (80)
Sherry, R., 188 (6), 194 (47)
Shi, Q. Z., 255 (71)
Shiemke, A. K., 20 (70)
Shigehera, K., 38 (27)
Shim omura, S., 59 (29)
Shimozawa, R., 224 (39)
Shimura, M., 26, 37 (13),143 (21),
249 (44), 274, 275 (7)
Shirahama, S., 364 (Ill b)
Shirokova, G. N., 89 (68)
Shoji, K., 204 (103)
Shore, S. G., 343 (109), 345 (118),
359 (61)
Showalker, K., 64 (63)
Showalter, K., 71 (114), 101 (188),
102 (197) (199), 103 (203)
Shriver, D. F., 261 (93), 262
(94-95)
Shteingarts, V. D., 313 (36-38)
Shtyrlin, V. G., 230 (83)
Shubochkin, L. K., 203 (10 I)
Shuikhina, L. P., 363 (102)
Shur, V. B., 366 (129)
Shvo, Y., 328 (42), 366 (132)
Siddhanta, S. K., 168 (58-59)
Siddiqui, S., 73 (141)
Sidebottom, P. J., 362 (95)
Sidem, P. K., 49 (102)
Siders, P., 8 (33), 10 (51), II (50)
Siebrand, W., 10 (98)
Siegel, J., 343 (107)
Siegel, R., 345 (113)
Sievert, A. c., 251 (55),315 (43)
Sigel, H., 228 (78)
igman, D. S., 73 (136)
Sik, V., 213 (148-149), 332 (66),
337 (83-86)
Silber, H. B., 219 (II)
Silverstre, J., 329 (48)
Simogi, R. H., 89 (64)
Simonova, T. A., 360 (74)
Simoyi, R. H., 68 (90), 197 (59)
438
Simpson, J., 254 (60)
Singh, A. N., 25, 27, 33, 35, 48
(101),62 (50)
Singh, B., 63 (55)
Singh, B. B., 63 (55)
Singh, B. P., 69 (98)
Singh, H. N., 62 (48)
Singh, N. H., 62 (49)
Singh, R. P., 63 (55)
Singh, V. C, 69 (97)
Singh, V. S., 64 (64)
Singleton, E., 207 (81), 242
(27-28),243 (29-30), 250 (51)
Sinou, D., 362 (95), 365 (123a-b)
Sipe, B. K., 94 (101)
Sisler, H. H., 93 (87)
Sisley, M. J., 154 (4), 216 (3)
Skelton, B. W., 113 (26),288 (56),
330 (54)
Skibsted, L. H., 210 (129)
Slater, S., 320 (3)
Smegal, J. A., 256 (77)
Smets, M. -N., 181 (110)
Smidova, I., 148 (37)
Smierciak, R. c., 142, 146 (19)
Smith, D. E., 34, 48 (99)
Smith, M., 49 (111)
Smith, R. S., 285 (48)
Smith, T. J., 20 (70)
Smith, W. B., 26, 36 (11), 145, 148
(29)
Smith, W. L., 16 (110)
Smyth, T., 352 (8)
Snipe, B. K., 360 (73)
Soares, A. B., 31, 45 (70)
Sobczak, J., 359 (65)
Sohn, M., 189 (11)
Solovykh, T. P., 203 (101)
Somorjai, G. A., 356 (43)
Sonnen berger, D., 255 (72), 258
(87), 259 (88-89)
Sostero, S., 128 (64)
Soulard, M., 100 (167)
Sowinski, A. F., 297 (90), 371 (157)
Soya, S., 188 (2), 230 (89)
Spangler, D., 326 (33)
Speier, G., 366 (131)
Spek, A. L., 112 (22)
Spellane, P. J., 211 (138)
Spiccia, L., 38 (25)
Spies, H., 189 (9), 190 (22)
Spinetti, M. C, 106 (6)
Spiro, C. L., 20 (70)
Spiro, M., 110 (7)
Spitsyn, V. I., 189 (16)
Spogliarich, R., 367 (136)
Spotswood, T. M., 217 (8)
Srinivasan, V. S., 24 (100), 25
(100-101),26 (100),27
(100-101),33 (101), 34 (100),
35 (100-101), 41 (48),
48 (100-101), 61 (42)(44),62
(49) (51), 93 (89)
Srinvastava, S. P., 69 (98)
Srinivasulu, K., 101 (187)
Sriram, R., 151 (48)
Staal, L. H., 339 (92)
Staley, R. H., 285 (46)
Stallings, M. D., 56 (19)
Stalteri, M. A., 113 (25)
Starn, C. H., 120 (47a)
Stamper, J. G., 81 (12)
Stanley, C S., 50, 51 (115)
Stansfield, R. F. D., 337 (87)
Staples, P. J., 142 (16)
Starzewski, K. A. 0., 120 (48)
Statler, J. A., 261 (92)
Staudigl, R., 80 (5-6)
Stedman, G., 87 (56),88 (59) (61),
91 (82),92 (84-85), 93 (84),99
(151)
Steele, K. P., 80 (8-9)
Steele, W. V., 99 (156)
Steenken, S., 55 (7), 66 (77)
Steiger, W., 16 (102)
Stein, C. A., 41, 47 (80)
Steinhaus, R. K., 228 (77)
Steinmetz, A. L., 328 (41)
Steinmetz, G. R., 356 (46)
Steinmetz, J., 218 (114)
Stenger, M., 232 (105)
Stepanovich, V. M., 209 (126)
Stephan, J. A., 21 (78)
Stephenson, G. R., 310 (28),311
(28) (31-33)
Stephenson, M., 250 (50), 305 (15)
Stephenson, T. A., 332 (63)
Stetsenko, A. I., 106 (1)
Stevenson, W. H., 82 (17)
Stewart, R. P., 68 (89)
Stille,J. K., 125(60),127(63),293,
295 (77), 296 (85-86)
Stimson, R. E., 261 (93)
Stobart, S. R., 110 (18)
Stockis, A., 294 (79)
Stockman, C., 304 (10)
Stone, F. G. A., 337 (87), 338 (90),
340 (96), 345 (116-117) (123)
Storm, C. B., 185 (122)
Stranks, D. R., 177 (94),193,194
(43)
Straus, D. A., 371 (156)
Strauss, S. H., 261 (93)
Strehlow, H., 217 (7)
Streitwieser, A., 328 (44)
Strekas, T. C, 202 (87)
Strich, A., 362 (91)
Stroganov, V. S., 374 (173)
Strohmeier, W., 366 (130)
Strona, L., 344 (110) (112)
Strukul, G., 361 (79)
Struntz, G. F., 258 (86)
Stults, B. R., 365 (120)
Stynes, D. V., 198 (62), 200 (70),
233 (109)
Suarez, T., 364 (113)
Sueur, S., 201 (82)
Sugi, Y., 354 (35)
Author Index
Sugimura, M., 159 (19)
Sulfab, Y., 70(107-108),101 (170)
Sullivan, B. P., 15 (113),202 (94),
204 (94) (107), 324 (21)
Sullivan, J. C, 62 (52), 97 (139)
Sullivan, T. R., 193, 194 (43)
Summers, D. P., 237, 246, 247 (5)
Summerville, D. A., 170 (68)
Sundaralingam, M., 177 (91-93)
Sundaram, P. M., 94 (99)
Sunjic, V., 364 (115)
Supa, B. K., 74 (147)
Sushila, J., 37 (12)
Sutin, N., 7 (31), 8 (35), 9 (31),11
(47-49), 12 (47), 13 (56), 15
(56) (107), 33 (87) (90), 34
(90),39 (34), 41 (34),48
(86-87) (90), 49 (108), 54 (12)
Sutton, C. A., 150 (46)
Sutton, J. E., 17 (69),18 (69-69a),
19 (69), 20 (69a)
Suzuki, K. Z., 72 (129), 170 (69)
Suzuki, M., 369 (147)
Sveshnikova, L. B., 209 (126)
Swaddle, T. W., 154 (4),199 (74),
216 (3), 220 (15)
Swallow, A. J., 97 (133)
Swamy, B., 363,(98)
Swanson, B. I., 22 (84)
Sweet, J. R., 356 (44)
Sweigart, D. A., 148 (35), 200 (78),
201 (80),233 (108) (111),
249 (49),301 (1), 302 (2), 306
(17),314 (39)
Swerdloff, M. D., 361 (85a)
Swisher, R. G., 142, 146 (19)
Switzer, J. A., 72 (128)
Sykes, A. G., 29 (61), 31 (70),32
(61),44 (60-61), 45 (70), 49
(109-110) (114), 50 (109)
(115),51 (114-115),56 (15)
Syrtsova, G. P., 159 (20)
Szalda, D. J., 189 (15)
Szalkiewicz, A., 360 (76)
Szecsy, A. P., 4 (12), 14 (108), 38
(29), 39 (32-33), 40 (29)
(32-33)
Taarit, Y. B., 362 (96)
Tabatabaian, K., 244 (34)
Tachiyashiki, S., 192 (37), 193
(38-39) (41)
Tagaki, W., 94 (96)
Taghizadeh, N., 372, 373 (165)
Takach, N. E., 177 (99), 182
(117)
Takahashi, M., 368 (143),370
(150)
Takakubo, M., 95 (111)
Takami, Y., 355 (35)
Takaya, H., 369 (145), 370 (150)
Takechi, K., 336 (78)
Takeguchi, S., 365 (119)
Takemoto, T., 114, 119 (34)
Author Index
Takeshita, K., 364 (I la-b), 375
(177)
Taketomi, T., 369 (145)
Takeyama, T., 96 (121)
Takinami, Y., 151 (54)
Talapka, M., 145 (31)
Tam, T. M., 98 (148)
Tam, W., 325 (29), 356 (45a)
Tamaru, K., 90 (73)
Tamblyn, W. H., 31, 43 (47), 282
(28)
Tampieri, M., 353 (l7a-c)
Tamura, K., 224 (40)
Tan, T. -K., 338 (89)
Tanaka, H., 123 (55a-b), 321 (10)
Tanaka, K., 31,46 (72), 74 (145)
Tanaka, M., 168 (57), 216 (2),230
(91) (93), 353 (18), 355 (36)
Tanaka, N., 26, 37 (13), 143 (21),
249 (44), 274, 275 (7)
Tanaka, T., 31, 46 (72)
Tanaka, Y., 285 (47)
Tanake, K., 96 (129)
Tandan, O. P., 26, 36 (10)
Tang, S. C, 354 (24)
Tang, T. W., 24 (8), 25 (7-8), 36
(7-8)
Tani, K., 369 (145)
Tanner, M., 17 (68)
Tapschoff, R. E., 37 (16)
Tapuhi, E., 227 (64)
Taqui-Khan, M. M., 72 (130), 363
(98)
Tarama, K., 362 (90)
Tarmak, M., 84 (25)
Tasker, R. F., 181 (Ill), 182(112)
Tatsumi, K., 125 (60), 293, 295
(77),351 (I)
Taube, H., 7 (30),14,15 (110),16
(64).17 (69), 18 (69-69a). 19
(69),20 (69a), 41, 47 (79), 200
(76),204 (106)
Tauzher, G., 169 (62)
Tavanaiepour, I., 256 (77)
Taylor, L., 72 (126)
Taylor, M. J., 333 (68), 345 (1I4)
Taylor, P. G., 84 (29)
Taylor, R. B., 369 (146)
Tebbe, F. N., 371 (156)
Tembe, B. L., 4 (9)
Templeton, J. L., 326 (38)
Terai, Y., 282 (29)
Teranishi, S., 361 (87), 364 (108)
Teuben, J. H., 329 (49),331 (58)
Thayer, J. S., 182 (116), 281 (25)
Thies, W. R., 20 (70)
Thirst, A. J., 206, 209 (115)
Thoi, H. H., 372 (164)
Thomas, M. G., 358 (53a)
Thomas, V. M., 101 (177)
Thompson, L. D., 123 (56), 332
(63)
Thompson, M., 145 (26)
Thompson, M. S., 201 (83)
Thompson, R. c., 69 (102-105), 70
(102-105),98 (143-145), 99
(157)
Thomson, M. A., 341 (IO!)
Thorn, D. L., 294 (79),371 (156)
Thornback, J. R., 190 (20)
Thornley, R. N. F., 66 (82), 188 (3)
Thornton, A. T., 31, 45 (70)
Threlkel, R. S., 268 (III), 340 (95)
Thyagarajan, G., 94 (103)
Tietavainen, G. M., 74 (148)
Timmer, K., 19, 20 (71)
Tinnemans, A. H., 19,20 (71)
Tinner, V., 161, 162 (35)
Tipper, C. F. H., 298, 299 (92)
Tiripicchio, A., 121 (52),343
(107), 345, 346 (125)
Tiripicchio Camellini, M., 343
(107)
Tkaczuk, M. N.,216(4-6),217(8),
218 (4-6)
Tkatchenko, I., 374 (175)
Tobe, M. L., 3 (7), 106 (4), 116
(36-39), 117 (40-41),
161 (28), 162 (37), 163 (28),
212 (146)
Tobias, R. S., 127 (62)
Todd, L. J., 242 (25)
Toma, H. E., 196 (56)
Tomita, H., 72 (132)
Tomiyasu, H., 188 (2), 230 (89)
(92)
Tomkins, I. B., 288 (56)
Tondeur, J. J., 81 (14)
Tondre, c., 225 (47-48)
Tonge, J. S., 21 (78)
Toniolo, L., 354 (25) (30)
Topalsavoglu, N., 352 (l4a)
Tordo, P., 79 (2)
Torroni, S., 250 (52)
Tourog, B. S., 360 (76)
Townsend, J. M., 366 (126)
Traber, R., 10 (42)
Traficante, D. D., 335 (74), 352 (9)
Traverso, 0., 128 (64)
Treger, Yu. A., 360 (71)
Treston, A., 161 (34)
Trevor, P. L., 84 (27)
Trimm, H. H., 221 (21)
Tripathy, K. K., 157 (14)
Trogler, W. c., 243 (31), 244
(31-32),255 (71) (75), 321 (6)
Trogu, E. F., 199 (70)
Trop, H. S., 189 (15)
Trost, B. M., 369 (149)
Trotter, J., 365 (122)
Troupel, M., 295 (82)
Troy, W. C, 101 (182)
Try tko, R. L., 252 (56)
Tso, C c., 354 (32)
Tsou, T. -T., 183 (118), 276,277,
278 (14)
Tsoy, A. A., 317 (52)
Tsuchiya, M .. 227 (71)
Tsuchiya, R., 152 (58-59)
Tsukahara, K., 54, 55 (3-4)
Tsutsui, M., 351 (I)
Tubino, M., 192 (35-36)
Tucker, J. R., 325 (26-27)
Tufano, T. P., 199 (71)
Tulip, T. H., 371 (156)
Tunuli, M. S., 48 (93)
Turco, A., 294 (80-81)
439
Turgoose, S., 306, 307 (20)
Turner, H. W.,335(75),374(170b)
Turney, T. W., 333, 334 (72)
Tyrlik, S., 364 (107) (1I2)
Tzeng, D., 80 (9)
Uchida, A., 372, 373 (166)
Uchida, K., 151 (54)
Vchino, N., 368 (143)
Veda, Y., 359 (62)
Vehara, A., 152 (58-59)
V go, R., 351 (2), 364 (1I8)
U1strup, J., 6 (27)
Umemoto, K., 96 (114), 197 (58)
Vmoh, S. A., 193 (40)
Vnruh, J. D., 353 (19b), 354 (l9b)
(2Ib)
Vppal, J. S., 285 (46)
Ushio, H., 221 (21)
Vson, R., 339 (91)
Vysotskii, M. P., 353 (15)
Uzan, R., 366 (133)
Vaccher, c., 353 (19a)
Vagg, R. S., 202 (92-93)
Valencia, N., 364 (1I3)
Valentine, D. Jun., 366 (126)
Valentini, G., 355 (39)
Valiotti, A., 198 (63)
Vamaguchi, M., 63 (60)
Van Bolhuis, F., 331 (58)
Van der Linden, J. G. M., 19,20
(71), 112 (23)
Van der Ploeg, A. F. M. J., III
(19), 112 (21-24), 113 (24)
Van der Poel, H., 120(47-49),121
(50), 252 (58), 332 (67)
Van Derveer, D., 129(71),252(56)
Van Eldik, R., 38 (26), 89 (66), 106
(5), 122 (54), 124 (57), 131
(54), 149, 150 (42), 157 (12),
166 (48),167 (51-52),173
(79-80), 230 (87), 290 (65),
322 (14)
Van Eldite, R., 38 (24)
Van Etten, R. L., 89 (62)
Van Koten, G., III (19), 112
(21-24),113 (24),120(47-49),
121 (50), 196 (S5), 252 (58),
332 (67)
Van Leeuwen, P. W. N. M., 374
(176)
Van Ommen, J. G., 375 (178)
Van Rens, J. G. M., 375 (178)
Van Santen, R. A., 359 (65)
440
Van Stein, G. c., 120(49),252(58)
Van Zijl, P. C. M., 163 (39)
Vandenunghen, G., 81 (14)
Vani, P., 68 (91), 89 (63), 99
(152-153)
Vanquickenborne, L. G., 193 (42),
210 (131)
Varen, M., 189 (16)
Varescon, F., 360 (66)
Vari, P., 60 (38)
Vaughan, D. H., 206, 209 (115)
Vaughn, J. W., 142 (18), 147 (33)
V celak, J., 360 (75b)
Venkataro, K., 69 (97)
Venkatasamy, R., 60 (37)
Venkatasubramanian, N., 61 (44)
Ventori, M., 48 (8)
Venturi, M., 48 (8)
Venturini, M., 220 (18),227 (65)
Venzo, A., 316 (49), 332 (60)
Verani, G., 60 (36)
Verrall, R. E., 219 (12)
Vicente, R., 166 (49)
Vichi, E. J. S., 192 (35-36)
Vickrey, T. M., 70 (109)
Vieras, F., 189 (10)
Vigee, G. S., 361 (85b)
Vijayaraghavan, V. R., 28 (21), 29
(21-22), 37 (21), 38 (22)
Visca, M., 48 (97)
Visco, S., 237, 252 (4)
Viswanath, A. K., 16 (110)
Vitiello, R., 364 (118)
Vlcek, A., 148 (39)
Vlcek, A. A., 148 (39)
E., 10 (42)
Vogle, A., 48 (91)
Vogler, A., II (54), 13 (54-55), 14
(54-55), 203 (99)
VOg!, H., 263 (100-101)
Voitko, J., 361 (84)
Vojtko, J., 368 (142)
Vollhardt, K. P. c., 358 (5Ib)
Vollmer, S. H., 254 (63)
Vol'pin, M. E., 366 (129)
Von Deuster, E., 98 (148)
Von Deuten, K., 321 (8)
Von Holtum, A., 232 (103)
Von Philipsborn, W., 341 (99)
Von Sonntag, c., 97 (135)
Vorob'eva, T. P., 100 (166)
Vos, J. G., 202 (91)
Vrachnou-Astra, E., 64 (65), 274
(8),317 (53)
Vrieze, K., III (19), 112 (21), 113
(24), 121 (50), 196 (55), 339
(92)
Vuik, c. P. J., 200 (79),233 (109)
Waddington, T. c., 329 (47)
Wademan, R. J., 212 (143) (145)
Wagner, P. J., 202 (88)
Wahl, A. c., 4 (13),32,46 (77)
Wajda, S., 144 (24)
Walker, H. W., 238 (8), 255 (68)
Walker, N., 239 (13)
Walling, c., 74 (144)
Wallis, H. L., 67 (86), 91 (80a)
Walters, R. T., 150 (47),255 (65)
Walters, W. S., 199 (67)
Walton, D. R., 371 (161)
Waltz, W. L., 44 (59), 255 (65)
Wang, C. B., 231 (97)
Wang, C. L., 72 (128)
Wang, H. H., 354 (32)
Wang, L. -P., 292 (71)
Wang, W., 16 (101)
Wannowius, K. J., 232 (103-106)
Ward, B., 231 (97)
Wardell, J. c., 284 (43)
Warner, L. G., 179 (105)
Wasgestian, F., 149, 150 (42), 173
(79-80)
Wasserman, H. J., 335 (75), 345,
347 (124)
Watanabe, A., 188 (I)
Watanabe, F., 232 (101)
Watanabe, J., 21 (76)
Waterman, P .. 329 (50)
Watson, P. L.,373 (169)
Watts, D. W., 38 (25)
Watts, R. J., 210 (130), 211
(138-139)
Watts, W. E.,312(35),315(46-47)
Wautier, H., 181 (110)
Wax, M. J., 260, 261 (91)
Wayland, B. B., 356 (45b)
Weaver, M. J., 4 (14), 42 (39)
Webber, C. T., 130 (74)
Weber, J. H., 184 (119), 282 (27)
Weber, W., 207 (118), 208 (118)
(121)
Weber, W. P., 80 (8-9)
Webley, W. S., 159 (21)
Wegman, R. W., 254, 255 (64)
Wie, Ho-Hsiang, 194 (46)
Weiderhammer, K., 345 (113)
Weigert, F. J., 368 (139)
Weighardt, K., 38 (30)
Wein, M., 164 (43)
Weiner, M. A., 202 (87)
Weiner, W. P., 269 (115)
Weller, A., 10 (39)
Wellings, P., 69 (96), 195 (50), 196
(53)
Wells, C. F., 74 (142-143), 96
(126), 166 (47), 225 (50)
Wendlolski, J. J., 326 (33)
Wengrovius, J. H., 371 (l62a)
Wenninger, J., 91 (78)
Werner, G., 73 (135), 96 (128)
Werner, H., 113 (27), 328 (45-46)
Werner, R., 328 (46)
Wesolek, M., 370, 371 (153a-b)
West, B. 0., 72 (124)
West, D., 165, 166 (46)
Author Index
Westheimer, F. H., 93 (93-94)
Wherland, S., 29, 39 (37)
Whimp, P.O., 177 (95)
Whitbum, K. D., 3 (3)
White, A. H., 113 (26), 288 (56),
330 (54)
White, c., 244 (34)
White, M. A., 269 (115)
Whitesides, G. M., 124, 125
(59a-b), 285 (44), 293 (78),
297 (90-91), 298 (91), 299
(93-95), 371 (157)
Whittaker, D., 87 (44)
Wickramasinghe, W. A., 148 (38),
211 (137)
Wieghardt, K., 188 (4)
Wigzell, J. McM., 284 (43)
Wild, S. B., 121 (51),311 (34)
Wilke, G., 330 (52)
Wilkinson, G., 356 (43), 358 (52a)
Williams, B. L., 213 (148), 337
(85-86)
Williams, D. L. H., 87 (43)(47-49)
Williams, E. H., 221 (23) (25)
Williams, G. M., 286 (49-50)
Williams, M. L., 253 (59)
Williams, P. A., 199 (67), 202
(92-93),306,307 (19-20), 311
(33)
Williams, R. D., 26, 36 (II), 145,
148 (29)
Willis, c., 3 (I)
Wilson, I., 100 (162-163)
Wilson, M. T., 73 (137)
Wilson, R. B. Jr., 340 (94)
Wimmer, F. L., 128(65),212(147),
336 (79)
Winans, R. E., 99 (155)
Winfield, J. M., 199 (66), 231 (98)
Winter, M. J., 337 (87)
Wismeijer, A. A., 108 (9)
Wisseroth, K., 351 (4)
Wohlers, H. D., 192 (31)
Wojcicki, A., 255 (65)
Wolfe, S., 65 (75), 66 (76)
Wolff, T., 101 (171), 103 (205)
Wong, C. -L., 29, 42 (42),170 (70)
Wong, F. S., 288 (56)
Wong, K. Y., 16, 17 (62), 22
(90-91)
Wong, V. K., 356 (45a)
Wong, W. K., 325 (29), 356 (45a)
Wood, D. L., 272 (6)
Wood, J. M., 281 (24)
Wood, P. B., 37 (14)
Wood, T. G., 256 (77)
Woodford, R. c., 337 (81)
Woods, B. A., 356 (45b)
Woods, R. J., 44 (59)
Woodward, P., 337 (87), 341 (98),
345 (116) (123)
Woodward, S. S., 360 (70)
Woynar, H., 80 (7)
Author Index
Wrighton, M. S., 237 (5), 244 (33),
246, 247 (5)
Wroblewski, J. T., 14,22 (83)
Wuhrmann, J. c., 94 (102)
Wynberg, H., 351 (6)
Xu, X. D., 372 (164)
Yadav, S. K. S., 203 (95)
Yadav, K. D. S., 228, 229 (80)
Yakamoto, A., 293, 295 (77)
Yamabe, S., 5 (23), 54, 55 (5), 56
(17)
Yamada, S., 219 (12)
Yamada, Y., 360 (70)
Yamagata, T., 369 (145)
Yamagishi, A., 232 (101)
Yamake, S., 56 (18)
Yamamatso, S., 63 (60)
Yamamoto, A., 125 (60-61), 127,
128 (61), 295 (83-84), 322 (13)
Yamamoto, M., 54, 55 (5)
Yamamoto, N., 362 (90)
Yamamoto, T., 295 (83), 372,373
(166)
Yamamoto, Y., 44 (62), 54, 55
(3-4)
Yamanaka, T., 352 (II)
Yamatera, H., 160 (25), 192 (37),
193 (38-41)
Yamazaki, Y., 354 (33)
Yandell, J. K., 29 (63-64), 45
(63-65)
Yang, D., 143 (20)
Yang, D. B., 358 (55)
Yang, L. -W., 345, 347 (121)
Yang, X., 150 (46)
Yang, X. c., 151 (55)
Yano, Y., 216 (3)
Yasuda, H., 330 (53)
Yasunaga, T., 224 (40)
Yat, S. H., 198 (62)
Yemul, S. S., 93 (95)
Yokoyama, 0., 230 (92)
Yoneda, G., 292 (70-71)
Yoneda, H., 151 (51), 184, 185
(120)
Yoshida, N., 182 (113)
Yoshida, T., 359 (62)
Yoshihara, K., 190 (19)
Yoshihiro, S., 231 (96)
Yoshikawa, S., 63 (60)
Yoshikuni, T., 152 (58)
Youde-Owei, L., 53, 54 (2)
Young, D. A., 354 (2Ia)
Young, P. R., 101 (176)
Young, R., 366 (126)
Zahurak, S. M., 256 (79)
Zakharov, A. V., 230 (83)
Zakharov, I. V., 360 (74)
Zakharov, V. A., 373 (168)
Zakir-Ali, S., 23, 24 (2)
Zamudio, W., 73 (134)
Zanella, A., 164 (43)
441
Zanello, P., 130 (73)
Zassinovich, G., 366 (127) (134),
367 (135)
Zawacky, S. K. S., 7 (30), 41, 47
(79)
Zeigerson, E., 43 (51)
Zerbe, H. D., 205 (108-110)
Zerner, B., 161 (32-34)
Zetterberg, K., 330 (51)
Ziegler, M. L., 268 (113-114), 345
(113)
Zimmermann, H., 240 (20)
Zinato, E., 139 (13), 141, 146 (15),
150 (43)
Ziolkowski, J. J., 359 (65), 366
(128)
Zipp, A. P., II, 12 (47), 33, 34,148
(90)
Zollinger, H., 87 (53) (55)
Zombeck, A., 72 (131)
Zum Winkel, K., 189 (13)
Zwanziger, H., 73 (135), 96 (128)
General Subject Index
Acetaldehyde, from ethanol, 73
Acetic acid, Monsanto process, 290
Acetylacetone
deuteration of Co(I1I) complex, 184
exchange in [V(acac)l)' 187
manganese complexes, 189
palladium(lI) complexes, 115
[Tc(acac)J), 190
Acrylonitrile, hydrolysis of, 175
Actinides, oxidative addition to, 300
Activation parameters
for complex reactions, 215
see also Volumes of activation
Alcohols, oxidation of, 64
Aldehydes, decarbonylation of, 355
Alkenes
catalytic isomerization, 368, 369
hydrogenation of, 362
metathesis of, 370
oxidation of, 65, 66
polymerization of, 373-375
Alkylcobalamins, 182
,a-elimination in, 279
Aluminum(III), kinetics of complex
formation, 227
Amines
nucleophilicity of, 307
Aminolysis, of Co (III) glycine esters,
181
Ammonia
from [Mo(NH)] complex, 66
from.[Mo(N2MPMe2Phh),67
reaction with NO, 90
Ammonia, liquid
trans-[Cr(I,3-pn)2BrF)+, 147
Co(I1I), Rh(III) petammines, 163, 206
Anation of
cobalt(I1I) complexes, 166
[Cr(NHl)5H20+), 145
[Pd(Etldien)H20f+, 106
[Pd(Et4dien)H20f+, 106
Anchimeric effect, transition state
stabilization, 308
Antitumor complexes, review, 106
Aquation of
443
arsenic(V) ester, 95, 233
cobaJt(III) complexes, 153
cobalt(lII) sulfonate, 155
[Co(NHl)sFf+' 160
[Co(NHl)sROH)l+, 154
[Co(NHl)5S04f, 154
[Co(NHl)sNHS02NH2)2+, 155
[Co(NHl)5NH2CH2C02Hr, 160
[Co(NHl)sOlSFf, 165
[Co(NHl)4(CN)Xf, 155
[Coen2Br(NHl)2+, 158
[Coen2CI(imid)r, 159
[Coen2CI(benzotriazole)f+, 157
trans-{Coen2(DMSO)CI)2+, 157
trans-{Coen2(H20)Cli+, 157
[CoCI(tren)NHlf+, 159
[CoCI(trien)(benzimid)]2+, 157
[CoCh(cyclam))+, 156
[Co(CNh)l-, 173
Cr(I1I) ammine complexes, photoaquation,
149
[Cr(NHl)4(CNhf,141
444
Aquation of (cont.)
[Crenl]J+, 150
trans-[Cren,F,f, 141
[Cr(H,O)S02CCChf, 138
[Cr([12]aneN.)Ch]'+, 142
[Cr(malh(H,6),L 144
[Fe(bipYhf\ isotope 194
[Fe(Xphenhf\ 199
[Fe(CN)sSOlt, 190, 191
Rh(III) complexes, 206, 207
[Rh(NHJ)sX]'+, 209
ruthenium(lI) phosphites, 200
ruthenium red, 204
[Ru(bipY)J]2+, 202
[TcCk.f-, 189
Aquocobalamin, 169; see Cobalamins
Arenes
coordinated, reactions, of, 312
hydrogenation of, 363, 364
Arsenic(V), ester hydrolysis, 95, 233
Aryl transfer, from Hg to Pd, III, 112
Ascorbic acid, as reductant, 53, 55
Asymmetric hydrogenation, 364, 365
Autocatalysis
of[Pth L,] reactions, 322
in square planar isomerization, 124
see also Catalysis
Azide ion
charge transfer, 174
Co(III) complex decomposition, 174
coordinated, reactions of, 177
intermediate in N2H. + HN02, 90
quenching singlet oxygen, 91
reaction with [Mn(COhC6H6f, 314
reaction with [WF6], 188
Barbier synthesis, 285
Barbituric acid, 201
Base catalyzed, deuteration of diketonates,
184
Base hydrolysis of
chromium(III) complexes, 151, 152
cobalt(III) complexes, 160-165
cobalt(III) sulfonates, 155
Co(III) chiral pentamines, 161
[Coen,CI(benzimid)]'+, 163
[Coen,X(etaH)]'+, 163
[Co(bamb)( dapo)X]'+, 162
[CoCI(3,2,3-tet)aminef+, 162
[CoCI(trien)(benzimid)]'+, 157
[Co(tren)(OH)(OCO,)], 167
Base hydrolysis of (cont.)
coordinated acetylphosphate, 175
coordinated acrylonitrile,
[Fe(4Mephen)J]'+' 194
coordinated esters, 107
platinum(lV) complexes, 211
rhodium(III) complexes, 206
silanes, 81
Benzyl group migration, 259
Beryllium(lI), ligand exchange, 2 I 6, 217
2,2'-Bipyridine
with [Fe(CN)6]-, 192
with pertechnetate, 190
[Ru(bipY)l]'+ deprotonation, 201
Bisulphite, dimerization to S,O/-, 98
Boron
BH. - fluxional ligand, 332
BH. - radical rections, 79
BH.- reduction of [Fe(CN)6]'-, 79
see also n.m.r.
Bridged complexes
binuclear Pt(II), 129
dichromium(II1) complexes, 144, 145
Briggs-Rauscher reactions, 102
Bromate ion, in oscillating reactions, IO I, 102
catalysis
ferrocynyl cation deprotonation, 316
see also Catalysis, correlations
Buchler's stability index, 198
Calorimetric studies
metal ions and peroxydisulfate, 195
on [Rh,(butyrate).], 210
Cannon's ellipsoidal model, 4
Carbene, attack on by P, 301
Carbinolamine, via intramolecular
cyclization, 177
Carbonic anhydrase inhibitors, 155
Carbon monoxide, activation of, 352
Carbonylation, of benzylalcohol, 355
Carbonyl hydrides, substitution in, 238
Carbonyl insertion, 259
Carbyne complexes, CO substitution, 240
Catalysis
of acetyl phenyl phosphate hydrolysis, 175
by Ag, in H1PO, oxidation, 68
by Ae+, in [Co(NHJ)sF]2+ aquation, 160
in alkene hydrogenation, 362, 363
in alkene isomerization, 368, 369
in arene hydrogenation, 363
autocatalysis, planar isomerization, 124
Catalysis (cont.)
of carbonyl substitutions, radical, 242
catalytic hydrogenation review, 271
clusters in homogeneous systems, 351
by Cu'+, in ascorbic acid oxidation, 55
in malic acid oxidation, 69
of dehydrogenation reactions, 366, 367
electron catalys is, 212
electron transfer chain, 237
by F in [Cr(LL),F2f aquation, 142
by H+, [Cr(CN)2(H20hNO], CN- loss, 138
by H+, (CH3hSiCR,CR,OH elimination, 83
by Hg2+
[CoCl(trien)(benzimid) ]2+ aquation, 157
[CoCI(tren)NH1]2+, aquation, 159
[CoClen,(imid)]'+, aquation, 157
[CoCI(3,2,3-tet)amine]'+, aquation, 159
[Co(NH3)sX]2+, aquation, 160
[Cr(H20)5CH20H]2+, hydrolysis, 275
[Fe(CN)6]4-, dissociation, 192
by iodine, exchange at silicon, 82
by metal ions, cis-[Cr(mal),(H,O),r
aquation, 144
by micelles, [Fe(phen)3]'+ reactions, 192,
193
by MeLi, [PdMe,L2] isomerization, 322
by nitrate, [Co(en),(H20)2]3+ anation, 167
by nitrous acid in nitration, 83, 84
of organic reactions, 351
by osmium in periodate oxidations, 71
of peroxomonosulfate decomposition, 97,
98
by ruthenium, in ketone oxidation, 203
of skeletal rearrangements, 369, 370
by thiourea, in nitrosation, 87
by Zn'+, [CrL3]2+ dissociation, 152
by Zr(IV) in [OsF6t substitution, 204
by Zr(lV) in [ReF6t substitution, 190
see also Chain reaction, ion-pairs
Catechol, oxidation of, 55, 56
Chain Reactions
alkene metathesis, 371
carbonyl substitutions, 239
Co (III) in [Coen3]1+ reactions, 174
[Cr(H,O)sR]'+, auto-oxidation, 135
electron transfer catalysis, 237
[Fe(CO)J(AsPH3),] + CCL, 287
Fischer-Tropsch reactions, 357
HgRX + R,CNO,-, 284
oxidative addition to [ZrCp2L,], 285
Chelate ring size, in Pt(lI) diamines, 117
Chiral
organometallic cations, 311
phosphines in hydroformylation, 354
Chlorine dioxide, 100
Chlorite-S,O,'- oscillating reactions, 102
Chlorous acid, 100
Chromium(III)
[Cr(H,O)sH]'+ formation, 133
Cr-C cleavage, 71, 72, 272-275
in oscillating reactions, 10 I
review, 133
Chromotropic acid, Al (III) complex
formation, 226
Citrate, Tc(V) complexes, 189
"Clock" reaction, 100
Clusters
bridging ligand motion, 345-349
carbonylation of [RhdCO}Jo]'-, 344
carbonyl migration, 342
445
carbonyl substitution reactions, 252, 257
hydrogen migration, 345
Cobalamins,275
alkyl, ,B-elimination, 279
Cobaloximes, 169, 275
Cobalt-carbon bonds
formation and fission, 275-281
transmethylation to Sn(II), 281
Conducting spheres model, 4
Conductivity of solid complexes, 21
Coordinated ligand reactions
of Co(III) complexes, 174-184
cyclobutadiene, attack on, 306
electrocatalysis of substitution, 245, 246,
252
halogenoarenes with alkoxide, 312, 313
of hydrocarbons, 301-318
hydrolysis of Pd(lI) esters, 107
methylation of thiolates, 147
Copper(III) tetraglycine
red uction of, 59
sulfite oxidation, 98
Correlations
acidity, [Cr(LL),F,f, 141

amines to 1)s-dienyls, 307, 308
Co (III) acetate hydrolysis, 179
[Cr(TPP)(L)X] stability, 147
ferrocenyl deprotonation, 316
charge transfer spectra, ion-pairs, 39
Gutmann donor number, Be(II) exchange,
217
446
Correlations (cant.)
Hammet parameters
[Cr(H,O),R]2+, 136
[Cr(H20),R]2+ benzoic acids, 168
Pd(O) oxidative addition, 295
HOMO energy and reduction potential, 5f
LFER, Sc(m) ligand exchange, 219
Ritchie's equation, 302
single ion hydration enthalpy, 192
Taft parameters, [Ni(Xbipy),]2+, 226
Tolman, oxidative additions, 292
Tolman scale, phosphine ligands, 306
Counter-cation effect
addition to 1)5 -dienyl, 310
see also ion-pair
Covalent hydration, 196, 199,210
Cross reactions, redox, 4
Cryptates, formation, dissociation, 222, 223
Crystal-field energy, vs. distortion, 147
Cyanide ion
[Cr(CN)6]3- photochemical loss, 149
with [Fe(Mephen)J]2+, 194
with [Mn(CO)J(C,H6)f, 314
from thiocyanate, 58
with [WF6], 188
Cyanoacetic acid, Co(m) complex, 175
Cycloaddition reactions, 318
Cyclobutadiene, attack on, 306
Cyclophosphazenes, 94
Cysteine
Fe(CN)s complex, 191
oxidation of, 59
Tc complexes, 189, 190
Decarboxylation, of aminoacid by Co(III),
63,64
Deprotonation
of [Coen2Cl(benzimidazole)]2+, 163
of [Coen2(NH2CH2CN)X]2+, 164
of [Mo(NH)X(dppe)2], 188
of [Ru(bipYh]2., 201
see also base hydrolysis
Dehydrogenation, catalytic, 366
Deuteration
of Co (III) amines, 163
effect on [Co(NH3 )6]3+/2+ potential, 9
exchange in binuclear arenes, 317
of [Ru(bipY)3]2+, 201
see also isotope effect
Diastereoisomers, trans-[ CoCL2(cyclam)f,
156
Diimine, N2 reduction intermediate, 67
Dinitrogen
reactions of, 67, 376
see also nitrogen
1,3-Dioxolane, from syn gas, 357
Discrimination, of intermediates, 200
Dodecylpyrazinium chloride, 193
Donor number: see Gutmann
EDTA, reactions of [Cr(EDTA)Rt, 143
Eight-coordinate Pt(lV), 213
Electrocatalysis, substitution via cationic
chain, 245
Electron catalysis, 212
Electronic Raman spectroscopy, 22
Electron transfer
excited organic species, 10
mixed valence complexes, 16
in solids, 21
Electrophilic attack on coordinated arenes,
317
Electrophilic substitution, aryl from Hg to Pd,
III, 112
Elimination from platinum complexes, 124,
125
Endo-addition to [Fe(CO)3(C7H9)f, 308
slow isomerization,
[RuCp(CO)allyl], 327
Esters from alkene carbonylation, 355
Ethanol
from glyme solvents, 358
from methyl formate, 356
oxidation to acetaldehyde, 73
Ethylene insertion into Co-H, 332
Exchange reactions
of acac in [V(acac)J], 187
of cr in cis-[Coen2CICNf, 170
of F in V(lV) complexes, 230
of H in Co(III)ammines, 163
of H20 in [Pt(H20),]2', 109
of malonate in [V(mal)3]3-, 188
in manganese(III) complexes, 189
of Me in [PdMe2L2], 322
of 0 in No,-, 89
of 0 in TcO" 190
of 0 in J.L-peroxo Co(m), 171
of oxalate in [VO(OX),]2-, 230
of solvent in Co(ll) complexes, 23 I
of solvent in Co(III) complexes, 168-170
of solvent in labile complexes, 216-222
of solvent in [M(PR3)2(sol)2H2]', 208
Ferredoxin, models, 21
Fischer-Tropsch reactions
alkylation of benzene, 358
reviews of, 356
Five-coordinate compounds
d
6
, organometallic, 333
equilibria with [PtX,L,], 322
of gold(lII), 122
Mg(OPPhJ)" 217
of manganese(lII), 233
of nickel(II), 131
nonrigidity of, 322
of Pd(II) and Pt(II), 119
of rhodium(I), 121
of silicon, 82
Five-coordinate intermediates
in addition of CH3 I to Ir(I), 131
in anation of [Coen,(H
2
0),]3+, 167
in aquation of[Co(enh(H,O)CI]'+, 157
in aquation of optically active Co(IJI),
162
in axial-equatorial exchange, 323
in CO substitutions, 240
in [Cr(CO).{PPhJ)2] isomerization, 320
in cyc1ophosphazene reactions, 94
in manganate hexadiene oxidation, 66
in [Ruen,I,f photolysis, 203
in square planar isomerization, 122
Flash photolysis, of metal-metal bonds, 254
Flipping, diene intramolecular mechanism,
330
Fluorides, aquation of[Cr(LL)2F,f, 141, 142
Fluoroxysulfate, 70, 99
Formaldehyde, synthesis gas intermediate, 357
Formate, intermediate in water gas shift, 359
Formic acid, nitrous acid oxidation, 88
Frontier orbital control, addition to 1)5 -dienyl,
310
Gluconate, Tc(V) complex, 189, 190
Glutamate, Ni(II) complex, 224
Glutathione, 191
Glycine, reaction with [Cr(H,O)6f+, 145
Glyoximate complexes
Co(III) complexes, 182-184, 276
iron, axial ligand exchange, 198
methyl rhodium complex, 200
redox reactions of, 39
Gold(IlI), four jfive coordination, 121, 128,
129
Grignard reagents, 285
Ground-state distortion of Cr(Ill) Schiff
base, 146
Gutmann donor number, 217, 222
in reactions of Pd(ll), 108
Halide ion, oxidation of, 56, 57
Halogen exchange, at silicon, 82
Hammett relationships
447
[Co(en)2CI(H20)]'+ with benzoic acids, 168
see also Correlations
Heterolytic activation, 286
High pressure n.m.r., peroxo V(v) formation,
230
Homologation, via carbonylation, 355
Hydrazine
from nitrogen, 67
nitrous acid scavenger, 85
Hydrocarboxylation of alkenes, 355
Hydroformylation of alkenes, 352-355
using chiral phosphines, 354
mass transfer limitations, 353
photochemically induced, 352
of styrene, 354
Hydrogen migration over bridged metals,
339, 340
Hydrogen transfer reactions, 366, 367
Hydrogenation
of alkenes, 362, 363
of arenes, 363
asymmetric, 364, 365
of P(OCH3h, 358
Hydrogen peroxide
DMSO oxidation, 96
[Fe( diimine)J]'+, oxidation, 197
in oscillating reactions, 102
oxidation by [Ag(bipy),],+, 74
reduction of, 70
Hydrolysis
of BH. -, 79, 80
of Co(III) acetates, 179
of coordinated phosphates, 175-177
of [Cr(H,O),],+, 134
see also aquation
Hydrosilyation, 288
Hydroxylamine, decomposition, 91
Hypobromite, from OJ and Br2, 96
Hypochlorous acid, 100
Hyponitrite, 90
Inhibition of [Cr(H20)sR]'+ oxidation, 135
Initial state transfer parameters, 208
448
Inner-sphere reorganization, 6
Inosine, nickel complex, 224
Insertion reactions
of alkenes and alkynes, 265-268
of CO into metal-carbon bonds, 259-265
of ethylene into Co-H, 332
of sulfur dioxide, 268, 269
Intermediates
cobalamin decomposition, 280
cobalt(lV) macrocycle, 282
formaldehyde from syn gas, 357
formate in water gas shift, 359
in hydroformylation, 323
20-electron species, 237
Wheland sigma complex, 309
in Ziegler catalysis, 374
Intermediates, five-coordinate
photoaquation of Rh(III), 210
from [RuX2(C,H6)(dmso)], 200
see also Five-coordinate intermediates
Intervalence transfer bonds, 47
at coordinated sulfur, 212
at four coordinate silicon, 82
at octahedral centers, 202
10dine(lV), from iodate photolysis, 101
lon-pairs
buffer ion effects, 138, 139
charge-transfer bond correlation, 39
in [CO(NH3).(H,O),r anation, 167
in [CO(tren)(NH3)CI]2+ aquation, 159
in [Co(trien)(H,O),]3+ anation, 166, 167
in [Fe(CN)6]4- reduction, 38
ureactive, with SO/-, SO/-, 172
Iron(II)
diimine complexes, 192
high-spin 15-ane complex, 198
oxidation of, 37-42
Isomerization
of Co(III) complexes, 168-170
of trans-[Co(en)(DMSO)CI]'+, 169
of trans-[CoCI(cyclam)H,Of+' 157
during cis-[Cr(NH)).(CN),f preparation,
141
of [Cr(NH)4(DMF)CI]'+, 150
of [Cr(ox),(H20),r, 151
of [Os(PP),Ch], cis / trans, 204
of[PdL,R2], cis /trans, 295, 296
of [PdMe2L,], MeLi induced, 322
of [Pd(NCS)(SCN)L,], linkage, 108
of[PdP,X,], photoinduced, 128
of ruthenium(II) complexes, 202
of Ru(III) 7-methylhypoxanthine, 203
Isomerization (cont.)
of silicon compounds, 81-83
of square planar complexes, 122-129
Isonicotinamide, 204
Isotope effect deuterium
addition to [CO(CN)5]3-, 288
alkyl cobaloxime decomposition, 279
aquation of[Fe(bipY)3]2+, 194
cryptate dissociation, 223
decomposition of [PtL,R,], 299
dimethyl silene insertions, 80
elimination from [Pt,H3dppmf, 299
exchange in binuclear arenes, 317
exchange in coordinated C5Me5, 303
ferrocenyl deprotonation, 316
life of singlet oxygen, 95
protonolysis of [Cr(H,O)5H]2+, 133
Isotopes
in carboxylic acid oxidation, 62, 63
in [Ru(NO,),(CO,(PPh3),]
decomposition, 68
lOB, exchange in (BX),S3, (BY),S), 80
36CI, exchange in [Co( en),(CI)CNf, 170
15N hydrazine with nitrous acid, 87
18
0, acetyl phosphate hydrolysis, 175
18
0, [Co(en),(H,O)glyOH]3+ cyclization,
179, 180
18
0, exchange in /-L-peroxy Co(lII), 170
see also n. m. r.
Jack Bean urease, 161
J ahn-Teller distortion, in Cu(II) reactions,
229,230
Ketones, periodate oxidation of, 203
Labels
labelled nitric acid in nitration, 85
see also isotopes
Lactonization, Co(III) promoted, 178-181
Ligand exchange, see Exchange
Laser, induced dissociation, 191
Magnesium, five-coordinate, 217
Magnetic moment
high-low spin change in Fe(IJ), 199
of iron(II) diimine complexes, 194
Malic acid, catalytic oxidation of, 69
Malonic acid, in oscillating reactions, 102
Malononitrile, Co(III) complex, 175
Mandelic acid, oxidation of, 63
Marcus-Hush model, 3-6, 55
Markownikoff addition, amines to bound
olefins, 304
Medium effects
in redox reactions, 5
see solvent effects
Meisenheimer intermediates, in bound
halogenoarenes, 312
Mercury
catalyzed aquation: see Catalysis
Hg
2
+ with [Cr(H20)5CH
2
0R]2+, 134, 135
Metal carbonyls, ligand site exchange,
319-321
Metal-metal bonds
carbonyl migration, 337
flash photolysis of, 254
hydrogen migration, 339
metallocycloalkanes
in olefin metathesis, 372
thermal decomposition of, 289
Metallocyclopentene, in flipping mechanism,
330
Metalloproteins, redox reactions of, 49-51
Metal migration, in organometallics, 330
Metathesis, of alkenes, alkynes, 370-373
Methyl cobalamin, 42, 182
see also Cobalamins
Methyl exchange in [PdMe2L2], 322
7-Methylhypoxanthine, Ru(III) complex, 203
5- Methyltetrazole, from N3 and CHlCN, 178
Methyltransfer from Co(III), 184
Methylviologen radicals
in Co(I1I) reactions, 174
superoxide generation, 96
Micelles, [Fe(phen),]2+ dissociation,
racemization, 192, 193
Michaelis-Arbuzov rearrangement, 94
Migration
of benzyl group, 259
of CO, 337
of hydrogen, 339
of methyl from cobalt(III), 184
Mixed valance complexes, electron transfer
in, 16-21
Neighboring group participation, in nitrile
hydrolysis, 175
Nickel(O), oxidative addition to, 294
Nickel(II)
planar / octahedral, 228
planar /tetrahedral, 232
Nickel(III) complexes, 43, 44
Nickel(IV) complexes, 53, 58
449
Niobocene, hydride insertion reactions, 268
Nitramine, reduction to N2, 91
Nitration, of aromatic compounds, 85, 86
Nitric oxide, bonding to Fe(II), 227
Nitride, chromium (III) from azide, 151
Nitrile, hydrolysis of Co(III) complexes,
175
Nitrogen
n.m.r. review, 84
reactions of, 276
V(II) reduction of, 67
Nitrogen dioxide, to nitric acid, 86
Nitrogen monoxide, redox chemistry of, 90
Nitroprusside, photochemistry of, 192
N-Nitrosamines, 87
Nitrosation, 86-89
S-Nitrosothiouronium ion, 98
Nitrosoylazide, 88
Nitrous acid, 86-89
nitration catalyst, 84, 85
reduction of, 68
N.M.R.
l3C in intermolecular exchange, 320
complex reactions, temperature
dependence, 215
diarylditellurides, 12sTe, 99
H20 exchange at Fe
H
, 199, 220
high pressure anation of Pd(II), 230
high pressure exchange at Co(III), 217
high pressure solvent exchange, 216
of Ir(III) fast reactions, 208
of [MoS2(EtNOh), 188
of N
2
0
J
, 15N, 89
of nitration species, 85
nitrogen n.m.r. review, 84
of N02-, oxygen exchange, ISN, 89
of palladium phosphines, IIp, 108
of [PdCI(PEt,hL]\ IIp exchange, 110
of [PtL
2
(H
2
0),]2+, 195pt, 110
of [Pt(H20)4]2+, 19SPt, 109
of [Pt(SSh]2-, 19SPt, 110
[Re(CO)6f,
17
0 exchange, 242
silicates, 29Si, 84
of Tc04 -,
17
0, and 99Tc, 190
Nucleophilic attack
on coordinated hydrocarbons, 301
on coordinated olefins, 304
on coordinated phosphates, 176
by OH- on ligand, 175
Olefin: see Alkene
One-dimensional complexes, 21
450
Optical activity
[Fe(71-Cp*)(71-C6H6)]+' 315
see also Chiral
Optical electron transfer, 12-16
Oscillating reactions, 101, 102
Oxalate, exchange in [VO(oxht, 230
Oxidation of
ketones by periodate, 203
organic compounds, 359-361
Oxidative addition
enthalpies of, 292
reviews on, 271
theoretical treatment, 293
Oxygen exchange
at Be(II), 217
in N02, 89
in [Re(CO)6f, 242
in TcO.-, 190
see also isotopes
Oxygen scavengers, in Cr-C cleavage, 272
Ozone, carbonate solution of, 96
Palladium(II)
attack on by H-, Ph-, 305
catechol complex formation, 226
ligand substitutions, 106-108
Penicillamine, 189, 191
Peptide synthesis, Co(III) complexes, 181
Periodate, osmium catalyzed oxidations, 71
Peroxonitric acid, 84
Peroxydicobalt complexes, 170, 171
Peroxydisulfate, 68-70
calorimetric studies, 195
oxidation of [Fe(Mephen)3]2+, 194
oxidation of Fe
2
+, 97
Peroxymonophosphoric acid, 93
Peroxymonosulfate
decomposition of, 97
DMSO oxidation, 98
Phase transfer catalysis
carbonylation of PhCH(R)Br, 355
reviews of, 351
Phenyphosphatosulfate, hydrolysis of, 93,
94
Photochemical reactions
aquation of[CO(CN)6]3-, 173
aquation of[Cr(LL)J]3+, 150, 151
aquation of[Rh(NH3)5X]2+, 209
aquation of [Ru(bipY)3]2+, 202
aquation of rhodium complexes, 210
aquation of ruthenium complexes, 201
aquation of [TcCI6]2-, 189
carbonyl substitution reactions, 244
Photochemical (cont.)
decomposition of [Co(acac)2(N3)NH3], 174
isomerization of [PdP2X2], 128
isomerization of[ReCp(NO)(PPh3)], 326
N02, loss from 4-N02phen, 202
photochemistry of Co(III) complexes, 173
photochemistry of Cr(lll) complexes,
149-I51
photochemistry of Ir(I1I) complexes, 211
photochemistry of [Os(II)(terpy)LL]"+, 204
photolysis of [Ruen21z]\ 211
photolysis, flash, [Cr(H20)5Hf+
formation, 133
promotion of hydroformylation, 352
reduction of Cr(lll) polypyridyls, 37
Phosphato complexes of Co(III), 175-177
Phosphite complexes, 200
Phthalocyanine
iron(II) compound, 197
iron(II), Wperoxo complex, 198
iron(II), reaction with CO, 231
ruthenium(II), axial ligand substitution,
233
trans-effect in, 200
Platinacyclobutanes
as catalyst models, 352
decomposition of, 297
a-e1imination in, 335
Polyelectro1ytes, effect on complex
formation, 225
Polymerization, of alkenes, alkynes, 373
Polynuclear complexes: see Clusters
Polyvanadicacid gel, 21
Porphyrins
[Co(TPPS)(H20h]3- reaction with
pyridine, 173
oxidation of Co(III) complex, 72
reactions of Cr(lll) complexes, 147, 148
Pressure-jump
aluminum propionate, 226
BeSO. formation, 217
Pseudorotation, in Pt(II) ring closure, 117
Pulse radiolysis
alkyl radicals and [IrCI6]2-, 66
BrOi from bromate, 100
CI02 from chlorite, 100
of nitrate solutions, 84
or Xe03 solutions, 103
Quinols, oxidation of, 55, 56
Racemization
of Co (III) complexes, 168-170
Racemization (cont.)
of [Fe(phen)l]2+, [Fe(bipY)l]2+, 192, 193
see Isomerization
Radicals
[CrR]2+ as convenient source, 66
initiation of M-M reactions, 253, 254
metal atom reactions, 284
silicon, 80
see also chain reactions
Radical trap
n-CgHI7 SH, 188
cerium(II1), 69
hydrazine, 69
Radiolysis
see also Pulse radiolysis
of iodate, 101
Raman
electronic spectroscopy, 22
ruthenium red aquation, 204
Rapid injection n.m.r., 352
Reduction, induced carbonyl substitution,
240
Reductive elimination, cis-[PdL2R2], 295
Reorganization energy, 4, 43
Ring opening and closing
in acid catalysis of [Coen2(H20)glyO]2+, 180
of [Coen2(NH2CH2CN)Xr in base, 164
in [Cr(oxh(H20hr isomerization, lSI
of Ni(II)-ethylenediamine, 224
of [Ni(trien)(glycine)], 228
in Pd(lI) and Pt(II) complexes, 113-118
of Rh(II1) chelates, 209
Ring whizzing
of polyenes, 328
in [Ta(CpMPr")(1/2-C8Hg)], 331
Ritchie's equation, derivations from, 302
Rotational barriers
about metal-metal bonds, 325-329
calculation of, reviews, 328
intraligand, 326
from neutron scattering, 328
of [TaCb(PMelh] groups, 340
Ruthenium red, 204
Salt effects
aquation of iron(II1) complexes, 199
[Fe(phen)l]2+ racemization, dissociation,
192, 193
isomerization of planar complexes, 123
Scandium, ligand exchange at, 219
Schiff bases
iron(II) complexes, 194
rhenium complexes, 190
Second order reactions
anation of[Co(CN)l H20f-, 168
Be (II) ligand exchange, 217, 218
CO substitution reactions, 258
Fe (II) reaction with NO, 227
[Fe(CN)lLY- formation, 227, 228
nitric acid from N02, 86
nucleophilic attack at silicon, 82
oxidation, ArCH20H by Pb(IV), 65
[Pt(H20)4]2+ water exchange, 109
reduction of Ni(II1), 58
[SCk]l+, exchange reactions, 219
singlet oxygen disproportionation, 96
Selenium compounds, 99
Self exchange, redox, 4
Silanes
hydrolysis of, 81
radicals, 80
redistribution reactions, 81
Silicates, 29Si n.m.r. of, 84
Single-ion
hydration enthalpies, 192
transfer parameters, 196
451
Skeletal rearrangements, catalytic, 369, 370
Slippage, attack on olefin, 304
Solid-state reactions
of Cr(lII) complexes, 152
of metal trioxodinitrates, 89
Solvation, effect on activation volume, 194
Solvent assisted, CO insertion in
[MeMn(CO)l], 267
Solvent decomposition, ethanol from glyme
solvents, 358
Solvent effects
BeS04 formation, 217
[CO(CN)6]l- photoaquation of, 173
[Coen2BrNHl]2+ aquation, 158
[Co(NHl)lNCCHlr solvent interchange,
168
Cr(lll) amines, photoaquation of, 149
[Cr(NHl)lH20]l+ anation of, 145
[Cr(ox)2(H20)2r isomerization, lSI
cryptate dissociation, 223
[Fe(bipY)l]2+ reaction with 196
[Fe(bipy)2(CN)2] dissociation, 195
[Fe(phen)l]2+ racemization, 192, 193
[Fe(ClHlhf
fO
redox, Marcus model, 4
[Ni(bipy)]2+ formation, 225
[PdP2Me2], C2H6 elimination, 296
[Rhen2Cb]+' Hg
2
+ aquation, 208
[Rh(SR2)lCh] sulfide displacement, 209
ruthenium phosphite aquation, 200
singlet oxygen life-time, 95
452
Solvent effects (cant.)
square planar isomerizations, 321
Zn(II) ultrasonic absorption, 219
Solvent exchange
Co(ll) complexes, 231
Co (III) complexes, 168-171
trans-[Coen,(DMSO)CI]'+, 169
in labile complexes, 216-219
[Rh(PR3),(sol)H,f, 208
volumes of activation for, 220
Solvolysis
of Co(lII) complexes, 165, 167
of Fe (II) porphyrin, 198
of [Ru(NO,bipyht+, 202
see also aquation
Spin change in Fe(lI) reactions, 193
Spin trap, in BH4 - reactions, 79
Square planar complexes, isomerization, 321
Sta bilization
conjugated silicon transition state, 83
of ozone by carbonate, 96
Steric effects
barrier to metal-ligand rotation, 325
in Co-carbon bond cleavage, 227
in Cr-carbon bond cleavage, 272
Sulfite, iron cyanide complex, 191
Sulfonamide, complexes of, 155
Sulfoxide, Pt(II) complexes, I 15, I 16
Sulfur dioxide
insertion reactions, 268, 269
reaction with Co (III), 17 I, 172
as solvent, 188
Superexchange, in redox reactions, 6
Superoxide ion
in catalyzed H,O, reaction, 73
proton-induced disproportionation, 96
reduction of Co(lII) dimer, 66
Syn-anti allyl exchange, 329
T-jump, study of, Ni(lI)
planar /five / octahedral coordination,
DI
T-shaped intermediates, 125, 126
Tetraalkylammonium ions, effect on reactions
of [Fe(phenh]'+' 193
Tetrahedral Co(ll), substitution at, 232
Tetrahydroborate, BH4-
alkaline hydrolysis, 79
reaction with alcohols, 79
Thermal stopped-flow, 224
Thiocyanate, bridging ligand, 36
Thioethers, Co (III) complexes, 174
Thiols, with pertechnetate, 190
Thiosulfate, oxidation of, 60, 98
2-Thiouranacil, oxidation of, 59
Thiourea
nitrosation catalyst, 87
reaction with [Fe(CN)5H,Ot, 191
Tin-aryl bond cleavage, 284
Tolman's scale, 292
attack on cyclobutadiene, 306
Tracers: see Isotopes
Transalkylation
of aryl from Hg to Pd(II), III
from cobalt to nitrogen, 282
from methyl cobalamin to tin, 281
Trans-effect
in [Cr(NHJ)(H20)5]J+, \39
in Cr(lll) porphyrins, 147, 148
of DMF in [Co(DMF)(MeOH)5]'+, 232
of W in [Rh(PRJ),(sol),H2], 208
in Os (VI) halocomplexes, 205
in [PdCl,biL], 114
in [Rh(NHJ)sX]2+, 210
in ruthenium phosphites, 200
of S-bonded SCN, 108
Transferin, 189
Triflate, labile Co (III) complexes, 155
f3- Trimethylsilyl alcohols, elimination
reactions of, 83
Trioxodinitrate, 89, 90
Triphenylphosphite, hydrogenation of, 358
Tryptophan, ruthenium complex, 202
Tunnelling matrix element, 6
Ultrasonic absorption
of Ca'+ / sorbitol, 223
of Cu'+/ carboxylates, 219
of Zn'+/ cr and NO), 219
Uranium, exchange at [UO,(AcNEt,)5f, 221
Urea, effect on complex formation, 225
Vanadium(IV), F exchange, 230
Vanillomandelic acid, Ni(lI) complex, 224
Vitamin BI " and models, 71, 182-184
Volumes of activation
of labile complexes, 220
for solvent exchange, table of, 220
[Coen,CI,f reduction by Fe'+, 38
[Coen,CI,f aquation, 154
[Coen,(OH,),]J+ anation, 167
[Co(NHJ)5(ROH)t aquation, 154
[Co(NH3)sS04f aquation, 154
Volumes of activation (cont.)
Co(III) porphyrin + NCS-, 168, 230
Co(ll), CHlCN exchange, 217
Fe(III) water exchange, 199
[Fe(H20)6r, [Fe(H20)sOH]2+ water
exchange, 220
[Fe(Mephen)l]2+, reactions of, 194
[Fe(phenh]2+, spin change in, 194
[Pd(Et4dien)H20]2+, anation, 106
[Pd(Etldien)H20]2+ anation, 106
review of, 153
[RhCh(H20h]/Hg
2
+ aquation, 207
[Rh(NHl)sl]2+, aquation, 207
[Rhen2Chf, aquation, 208
V(V) peroxo complex formation, 230, 231
Water exchange
in [Cr(NHl)6-x(H20)xr, 139, 140
in [Cu(tren)H20]2+, 228, 229
Water exchange (cont.)
in Fe3+, 100, 220
in [Pt(H20hf+, 109
453
Water gas shift reaction, formate intermediate
in, 358
Water, photolysis, of, 49
Werner, synthesis of [Coen2(N02)Clf, 157
Wheland intermediate, 309
Woodward-Hoffmann rules, racemization of
[Fe(phen)l]2+, 193
Xenon difluoride, hydrolysis of, 103
Yttrium(III), ligand exchange at, 221
Ziegler catalysts, 374
Zeise's salt, H iickel calculations, 326
Zirconium, substitution catalyst, 190, 205

(M. V. Twigg (Auth.), M. V. Twigg (Eds.) ) Mecha PDF

Uploaded by

Document Information

Original Description:

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

(M. V. Twigg (Auth.), M. V. Twigg (Eds.) ) Mecha PDF

Uploaded by

Copyright:

Available Formats

Volume 2

You might also like