Topics Introduction Molecular Structure and Bonding Molecular Orbital Theory Molecular Symmetry Coordination Complexes Reactions of Metal

f Metal Complexes Organometallic Chemistry

Housecroft 6.11-6.13, 20.9-20.11, 25 Shriver and Atkins Chapter 7,14

Reactions of Metal Complexes Formation constants

the chelate effect Irving William Series Lability

Reaction Mechanisms
I, A, D Mechanisms a, d Rate Determining Step

Substitution of Square Planar Complexes

the trans effect

Substitution of Octahedral Complexes

Formation of Coordination Complexes typically coordination compounds are more labile or fluxional than other molecules

MX + Y

MY + X

X is leaving group and Y is entering group One example is the competition of a ligand, L for a coordination site with a solvent molecule such as H2O
[Co(OH2)6]2+ + Cl[Co(OH2)5Cl]+ + H2O

Formation Constants Consider formation as a series of formation equilibria:

M+L
ML + L

ML
ML2

K1 =

[ ML] [ M ][ L]

K2 =

[ ML2 ] [ ML][ L]

Summarized as:
M + nL MLn

n =

[ MLn ] = K1 K 2 K 3 ...K n [ M ][ L]n

Values of Kn Typically: Kn-1>Kn

Expected statistically, fewer coordination sites available to form MLn than MLn-1 eg sequential formation of [Al(OH2)6-x(F)x](3-x)+

Breaking the Rules Order is reversed when some electronic or chemical change drives formation
Fe(bipy)2(OH2)22+ + bipy Fe(bipy)32+

jump from a high spin to low spin complex Fe(bipy)2(OH2)2 t2g4eg2 high spin Fe(bipy)3 t2g6 low spin
N N 2,2'-bipyridine = bipy

Chelate Effect
Compare: K1 to 2 for:
M(OH2)22+ + en M(OH2)22+ + 2NH3 M(en)2+ + 2H2O M(NH3)22+ + 2H2O

Basically equivalent chemistry but for Cu2+ log K1 =10.6 log 2 =7.7 chelated complex is three orders of magnitude more stable chelate effect: the enhanced stability of a chelated complex over its non-chelating analog attributed to the change in entropy, chelation trades two restricted solvent molecules for one bound ligand

Ring Formation and Electron Delocalization Ability to form rings with metal center improves stability
particularly five or six membered rings

Additionally, ligands with aromatic rings can behave as pi acceptors and form back bonding complexes
N N Ru N N N N

Irving William Series Values of log Kf for 2+ ions including transition metal species Kf series for transition metals:
Mn2+< Fe2+< Co2+< Ni2+< Cu2+>Zn2+

Irving Williams Series Partially explained by electrostatics: smaller metal centre, same charge = greater charge density Based on electrostatics we expect stabilities which vary as:
Mn2+< Fe2+< Co2+< Ni2+ > Cu2+>Zn2+

Irving William Series gives Cu2+ more stable than Ni2+

Because of Jahn Teller Distortion

Ni2+ vs Cu2+ Kf

Stepwise Kf for displacement of H2O by NH3 ligands from aquated Ni2+ and Cu2+

Reaction Mechanisms of d Metal Complexes Weve been considering the equilibrium formation Rate is important for understanding coordination complex chemistry
Inert: species that are unstable but survive for minutes or more Labile: species that react more rapidly than inert complexes

Labile vs. Inert General Rules:

For 2+ ion, d metals are moderately labile particularly d10 (Hg2+, Zn2+) Strong field d3 and d6 octahedral complexes are inert .i.e. Cr(III) and Co(III) Increasing Ligand Field Stabilization Energy improves inertness 2nd and 3rd row metals are generally more inert

Ligand Field Stabilization Energy (LFSE)

Consider the energy of the d orbitals before crystal field splitting relative to the first three possible electronic configurations

LFSE for Oh Geometry

dn d1 d2 d3 d4 d5 d6 d7 d8 d9 d10 High Spin config t2g1eg0 t2g2eg0 t2g3eg0 t2g3eg1 t2g3eg2 t2g4eg2 t2g5eg2 t2g6eg2 t2g6eg3 t2g6eg4 FSE (o) -0.4 -0.8 -1.2 -0.6 0 -0.4 -0.8 -1.2 -0.6 0 Low Spin config FSE(o)

t2g4eg0 t2g5eg0 t2g6eg0 t2g6eg1

-1.6 -2.0 -2.4 -1.8

LFSE: e- configuration determines stabilization

Associative vs Dissociative Reactions Ligand substitution reactions are either associative or dissociative
Associative: reaction intermediate has higher coordination number than reactants or products lower coordination number complexes Rates depend on the entering group Dissociative: reaction intermediate has lower coordination number than reactants or products Octahedral complexes and smaller metal centers Rates depend on leaving group

Patterns of Reactivity Formation constants tell us about thermodynamics Kinetics requires a different measure: nucleophilicity
Ligand displacement are nucleophilic substitution reactions The rate of attack on a complex by a given ligand (Lewis Base) relative to the rate of attack by a reference base.

Rates span from 1 ms to 108 s

Ligand Labels for Nucleophilic Substitutions Three types of ligands can be important:
Entering Ligand: Y Leaving Ligand: X Spectator Ligand Species that neither enters nor leaves Particularly important when located in a Trans position, designated T

Reaction Mechanisms Associative - A (2 steps)

MLnX + Y MLnXY MLnY + X

Dissociative - D (2 steps)
MLnX + Y MLn + X + Y MLnY + X

Interchange (1 continuous process)

MLnX + Y Y--MLn --X MLnY + X

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Rate Determining Step also denoted associative or dissociative associative (lowercase a)

the rate depends heavily on the entering group
[PtCl(dien)]+ + I[PtCl(dien)]+ + Br[PtI(dien)]+ + Cl[PtBr(dien)]+ + Cl-

dissociative (lowercase d)
the rate is independent of the entering group
[Ni(OH2)6]2+ + NH3 [Ni(OH2)5(NH3)]2+ + H2O

Substitution of Square Planar Complexes substitution of square planar complexes is almost always Aa mechanisms
rate depends on the entering group rate determining step is the M-Y bond formation

impacted by the Trans effect

the ligand trans to the leaving ligand (X) can alter the reaction rate

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Square Planar Substitution: The Trans Effect when the ligand, T, trans to the leaving group in square planar complexes effects the rate of substitution If T is a strong donor or acceptor, the rate of substitution is dramatically increased why?
if T contributes a lot of e- density (is a good donor) the metal has less ability to accept electron density from X (the leaving ligand) if T is a good acceptor, e- density on the metal is decreased and nucleophilic attack by Y is encouraged

Trans Effect Strengths Trans effect is more pronounced for donor as follows: OH-<NH3<Cl-<Br-<CN-,CO, CH3-<I-<PR3 Trans effect is more pronounced for a acceptor as follows: Br-<Cl-<NCS-<NO2-<CN-<CO

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Using the Trans Effect Suggest a means to synthesize cis and trans [PtCl2(NH3)2] from [Pt(NH3)4]2+ and [PtCl4]2-

Square Planar Substitution: Steric Effects steric crowding reduces the rate of A mechanisms and increases D mechanisms simply a spatial phenomenon:
less room around the metal means that a higher coordination number transition state is higher energy eg cis-[PtXL(PEt3)2] rate varies with L pyridine > 2-methyl py > 2,6-dimetyl py

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Square Planar Substitution: Stereochemistry observing the final product stereochemistry can provide information on the mechanism and intermediate lifetimes

Square Planar Substitution: Volume of Activation changes in volume along a reaction pathway can be determined usually by observing reaction rate as a function of pressure a negative V suggests an associative complex

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Square Planar Substitution: Entropy of Activation the change in entropy from the reactants to the activated complex is S determined by the temperature dependence of the rate associative mechanism has ve S as expected from increasing order of the system by loss of freedom for the entering group without release of the leaving group

Substitution of Square Planar Complexes Trans Effect ligand trans to X can increase substitution if it is a good donor or acceptor Steric Effects bulky cis ligands reduce Y nucleophilic attack Stereochemistry cis/trans conserved for A mechanism unless activated complex is long lived V and S are both negative for A mechanism

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Substitution of Octahedral Complexes I is the most important reaction mechanism for substitution of Oh complexes but is it Ia or Id
recall it depends on the rate determining step being YM formation vs MX breaking associative (lowercase a) the rate depends heavily on the entering group dissociative (lowercase d) the rate is independent of the entering group

Eigen-Wilkins Mechanism The standard mechanism for Oh I substitutions reactions Based on the formation of an encounter complex Fast pre-equilibrium:
ML6 + Y {ML6,Y}

KE =

[{ML6 , Y }] [ ML6 ][Y ]

Followed by product formation:

{ML6,Y} product

rate = k[{ML6 , Y }]

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Eigen-Wilkins Mechanism II The rate expression can be written in terms of the KE so that:
rate = kK E [C ]tot [Y ] 1 + K E [Y ]

Where [C]tot is the total of all of the complex species If KE[Y] << 1 then the rate becomes:
rate = kobs [C ]tot [Y ]

Using Eigen Wilkins kobs = kKE so we can get k Now test k to see if it varies with Y or not so we can assign Ia or Id Whew! See table 14.6 for experimental data

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Oh Substitution General Rules Most 3d metals undergo Id substitutions

I.e. the rate determining step is independent of the entering group and primarily is the breaking of the MX bond

Larger metals (4d, 5d) lean towards Ia Also low d electron density encourages partly Ia characteristics

Oh: Effects of Ligands Leaving Group

Nature of X is important as expected for Id as bond breaking of M-X is the rate determining step

Spectator ligands (cis-trans effect)

No clear trans effect for Oh complexes In general, good spectator sigma donors will stabilize the complex after the departure of the leaving group

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Oh: Steric Effects on Substitution steric crowding around the metal centre favors dissociative activation Dissociative activation relieves crowding around the complex Steric crowding has been qualitatively and quantitatively explored
Tolman Cone Angle See Table 14.7

Octahedal Substitution and V

M(OH2)6 + H217O M(OH2)5(17OH2) + H2O

For I mechanism, V is not large but Ia tends to be ve, Id tends to be +ve decreasing d number shows tendancy towards Ia mechanism

M2+ Ti2+ V2+ Cr2+ Mn2+ Fe2+ Co2+ Ni2+

d elec. 2 3 4 5 6 7 8

V -4.1 -5.4 +3.8 +6.1 +7.2

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Oh Stereochemistry of Substitution More complicated than for Td complexes Example: cis- or trans- [CoAX(en)2]2+ cis complexes tends to retain cis trans complexes can isomerize depending on the spectator ligand, depends on geometry of the activated complex
Trigonal bipyramidal results in isomerization depending on where Y enters Square planar leads to retention of stereochemistry

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Isomerization Reactions
Similar to substitution reactions Berry Pseudorotation mixes axial and equatorial positions in a 5 coord TBP species Both square planar complexes which undergo A mechanisms or Oh complexes which undergo D or Id mechanisms involve a 5 coordinate state so isomerization is possible

Twisted Oh Isomerizations Oh complexes may also isomerize via twist mechanisms Does not require loss of ligands or breaking bonds, just depends on energy barriers between confirmations
Bailar Twist (a) Ray Dutt Twist (b)

Both occur via trigonal prismatic confirmation

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Twists

Redox Reactions Requires transfer of electrons in form of straight electrons

Like electrochemical cell, transfer from one metal to another Transfer of group of ligands along with their electrons to effectively reduce or oxidize a metal centre Shriver and Atkins: Chapter 14 Housecroft and Sharpe: Chapter 25

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Redox Reactions Two reaction mechanisms

Inner sphere Requires formation of bridged bimetallic species results in ligand transfer at the same time Outer sphere No bridging ligand involved Direct transfer of electrons between the metal centres

Outer Sphere Reaction Mechanisms Readily identified when no ligand transfer occurs between the species Easier to identify when complexes are inert with respect to ligand substitution Born Oppenheimer Approximation
Electrons move faster than nuclei Complexes reorganization can be considered in a separate step from electron transfer

Marcus Equation
Electron transfer requires vibrational excited states, shape of potential energy well determines rate of transfer

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Inner Sphere Reactions Require the presence of bridging ligands

Ligands with multiple pairs of electrons to donate

Cl-

C N-

N N

C N-

Rate of electron transfer is dependent on the ligands that are present See table 14.11 in Shriver and Atkins or table 25.8 in Housecroft and Sharpe

Inner Sphere Reaction Steps Formation of Bridged Complex

MIIL6
+

XMIIIL5'

L5MII XMIIIL5'

Electron Transfer
L5MII XMIIIL5' L5MIII XMIIL5'

Decomposition into Final Products

L5MIII XMIIL5' products L5MIII X
+

MIIL5'

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Rate Determining Step Usually the electron transfer step However formation of bridging complex or the decomposition could also limit the rate Where rds is electron transfer
Good conjugation could provide a simple path for the electron

Studied via construction of bridging ligand systems as models

Conclusions Reaction mechanisms

A basic description of different mechanisms for Ligand exchange Isomerization Electron transfer Emphasis on ligand substitution reactions Determination of I, A, D mechanisms a vs d activation

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