Organometallic Reactions and

Catalysis
SARI EDI C

Gain or Loss of Ligands

CO dissociation
In many cases to add another ligand.
Dissociative and associative mechanisms
More complicated reactions.

Dissociation of phosphine (steric effects)

cis-Mo(CO)4L2 + CO Mo(CO)5L + L
Figure 14-1 and Table 14-1 (Article)
Rate dependence on cone angle and other factors.
Reaction follows the first-order rate law.

Oxidative Addition (OA)

Increases the coordination number and the
oxidation state of the metal.
OA reactions of square-planar d8
complexes.
trans-Ir(CO)Cl(PEt3)2 (Figure 14-3)
Changes in CN and oxidation state

Reactions may occur between ligands due

to close proximity.

Reductive Elimination (RE,

reverse of OA)
Decrease in coordination number and
oxidation state of the
metal.
OA
(-C5H5)2TaH + H2 (5-C5H5)TaH3
RE

RE reaction rates are also affected by ligand

bulk. How? (Table 14-2)

Nucleophlic Displacement
(attack by a Lewis base)
A strong nucleophile would be a ligand with strong
electron-donating character.
Organometallic complexes can behave as nucleophiles
in displacement reactions (especially negativelycharged complexes).
[Co(CO)4]- + RX RCo(CO)4 + XRCo(CO)4 + CO R(C=O)Co(CO)4 (acyl complex)
R(C=O)Co(CO)4 +ROH R(C=O)OR + HCo(CO)4
(generates the ester from an alcohol).

Modification of Ligands
Insertion a molecular fragment appears to
insert itself into a metal-ligand bond.
Many reaction mechanism can be complicated.
1,1-insertion (both bonds are made to the same
atom).
illustrate

1,2-insertion (bonds to the inserted molecule

are made to adjacent atoms in that molecule).
illustrate

Insertion of Ligands
How is CO inserted in the complex shown
previously (1,1-insertion)?
Work through this and understand.

1,2-insertions

Hydride Elimination
Transfer of a hydrogen atom from a ligand
to a metal.
elimination is the most common type.
position on the alkyl ligand.

Stability
Alkyl complexes that lack hydrogens are more
stable.
Coordinatively saturated complexes containing
alkyl ligands are also more stable.

Abstraction
Removal of a substituent from a ligand in
which the coordination number of the metal
does not change (can be removed by an
acid).

Organometallic Catalysts
(hydroformylation)
Converting terminal alkenes into other organic products.
(oxo process) H and HCO are formally added across a double
bond.
Show reaction
Largest-scale industrial process that is homogeneous

Mechanism was suggested by Heck and Breslow in

1961.
Examine each step in the cycle and characterize the reaction
according to type.
18-,16-electron cycling is common.

Comments on the
Hydroformylation Mechanism
CO pressure has to be controlled carefully.
Why?
Rate-determining step is the insertion of the
olefin (alkene).
Main purpose of the reaction is to produce
butanal from propene.
CH3CH=CH2CH3CH2CH2CHO

Union Carbide Hydroformylation

Process
Contain Rh and bulky phosphine groups.
How will this affect the mechanism?
(Ph3P)3Rh(CO)H

In many cases, the linear/branched ration

needs to high.
The catalyst is also water-soluble.

Hydrogenation of Alkenes
Wilkinsons catalyst
Show reaction (alkenes and alkynes)

Show mechanism and discuss

Step 9 is slow, the sequence 123 is favored.
The rate determining step is insertion, 4.

The catalyst hydrogenizes terminal and internal

olefins.
Examine Table 14-3.

Hydrogenation Catalyst
Selective hydrogenation can be observed if the
ligand contains multiple double bonds.
Another hydrogenation catalyst, (PPh3)2Rh(CO)H, is
very selective toward hydrogenation of only terminal
olefins.
Asymmetric hydrogenation
If the catalyst, [L2RHS2]+, bears an optically active
diphosphane, prochiral unsaturated molecules can be
hydrogenated to chiral products (enantiomeric selectivity).
L-Dopa (treatment of Parkinsons disease).

Alkene Metathesis
Demonstrate
Propene and 1-butene (what are the 4 new products that may form
from methathesis?)

Ring-opening metathesis (ROM)

Chauvin mechanism is most widely accepted.
Involved a carbene complex
The carbene reacts with an alkene to form a metallocyclobutane
intermediate. The intermediate can either revert to reactants or form
new products.
Schrock metathesis catalysts are most effective and the most studied
(available commercially).

Ring-closing methathesis (page 545)

Heterogeneous Catalysis
Used much more
extensively in industry
than homogeneous
catalysts.
Robust at high
temperatures.
Easy to separate out the
catalyst.

Composition of Heterogeneous
Catalysts
Uniform bulk of the
high-surface area serves
as the catalyst.
ZSM-5 (zeolite)

Multiphase highsurface-area material

serves as a support for
the active catalyst.
Pt/Re on alumina

Surface Ligands
In many cases, the nature of the surface ligand is
inferred by comparison of IR spectra with those of
organometallic or inorganic complex.
Terminal and bridging CO.

Surface-Sensitive Techniqus
Temperature-programmed desorption (mass
spectroscopy).
Photoelectron spectroscopy (XPS and Auger)
Low-Energy Electron Diffraction (LEED)
Scanning Tunneling and Atomic Force
Microscopies.
Vibrational Techniques (RAIRS and HREELS).
Many othes.

Catalytic Steps
Many parallels can be drawn in comparison
to organometallic mechanisms studied
previously.
Chemisorption and physisorption
Similar to interactions present in complexes
with low oxidation states.
Physisorption and chemisorption.

Catalytic Steps
Similar to homogeneous
catalysis, there is also a
balance between strong
enough adsorption for the
reaction to occur and weak
enough desorption that the
species can be removed
for further reactions.
HCOOH CO + H2O
(on a metal surface)

Diversity of Sites
Real surfaces possess a
large diversity of surface
types. Each surface type
may have a different
reactivity and/or produce
different products.
Lower selectivity.
Most reactive sites.

Examples of Heterogeneous
Catalysts
Hydrogenation of alkenes on
metal surfaces.
H2 is dissociatively
chemisorbed
Ethylene is associated
Hydrogen adds to produce an
alkyl species
Another hydrogen atom
coordinates and ethane leaves.
Actual species produced

Ziegler-Natta Polymerization
TiCl4 + Al(C2H5)3
A titanium alkyl complex is produce.
Ethylene or propylene associates and inserts
into the titanium-carbon bond.
The 1,2-insertion continues.
Mechanism has proved difficult to understand.
In Miessler and Tarr

Fundamental Studies of
Hydrocarbons on Platinum Surfaces
The techniques used.
Reflection-absorption infrared spectroscopy.
Auger electron spectroscopy
Temperature-programmed desorption/reaction
spectroscopy.
Others as needed.

Reflection-Absorption Infrared
Spectroscopy (RAIRS)
The dynamic dipole moment must have a component normal to the
surface to be visible.
The intensity of the vibration signature reveals orientation
information.
Position of the signature indicates identity of species on the surface.

_
q(t)
+

qcos
+
_

+
_
+
_

qsin

A Typical RAIRS Spectrum

The Labeling Study

Cyclic C8 Systems on Pt(111)

.

250-325 K
cyclooctene
cyclooctenediyl
C8H12
C8H14

1,3-cyclooctadiene
C8H12

.
250-300 K
1,5-cyclooctadiene
C8H12

. or
cyclooctadienediyl
C8H10

cyclooctatetraene

1,5-dihydropentalene

Stable to ~500 K,
decomposes to yield
predominantly surfacebound carbon,
hydrogen desorbs.

cyclooctatetraene
C8H8

bicyclo[3.3.0]2-octene
C8H12

Pentalene
C8H6

1,5-dihydropentalene
C8H8

1,4-Cyclohexadiene on Pt(111)

Hdistal
Hproximal

Hdistal
Hproximal