Ch 12 Inorganic Reaction Mechanisms

I. Introduction
A. Parallels to Organic Chemistry
1) Many terms and concepts are the same as in organic mechanisms
2) Complex geometries are more common in inorganic complexes
a) More rearrangements are possible
b) More isomers are possible
3) Not all metal ions react alike; all carbon atoms do
B. History and Goals
1) Werner and Jorgenson discovered many of the basic reactions
2) Experimentation over many years has yielded proposed mechanisms
3) Mechanisms can’t be proven, only disproven
a) We can’t directly observe individual molecules react
b) Evidence either supports a mechanism or rules it out
4) Goal: synthesize the predicted products by choosing the appropriate
reaction conditions.
C. Types of Reactions:
- Substitution,
- Oxidation/Reduction,
- Ligand Reactions
II. Substitution Reactions
A. Inert and Labile Complexes
1) Labile Complexes = those undergoing substitution with t½ < 1 minute
a) Many analytically useful reactions are labile substitutions
[Cu(H2O)6]2+ + NH3 [Cu(NH3)4(H2O)2]2+ + H2O
[Fe(H2O)6]3+ + SCN- [Fe(H2O)5(SCN)]2+ + H2O

b) Lability is generally a function of the metal ion, not the ligands

[Fe(H2O)5(OH)]2+ + H+ [Fe(H2O)6]3+
[Fe(H2O)6]3+ + Cl- [Fe(H2O)5Cl]2+
[Fe(H2O)5Cl]2+ + PO43- Fe(H2O)5PO4
Fe(H2O)5PO4 + SCN- [Fe(H2O)5(SCN)]2+
[Fe(H2O)5(SCN)]2+ + F- [Fe(H2O)5F]2+

c) Often, the reaction happens at the diffusion limit = as soon as the reactants
are mixed, they are done reacting. Diffusion = 1011 s-1

d) Labile Metal ions = those with small or zero LFSE

a) d1, d2, d7, d9, d10
b) High spin d4-d6
 2) Inert Complexes = those undergoing substitution with t½ > 1 minute
a) Inert does’t mean unreactive; Inert doesn’t mean thermodynamically stable
b) Inert does mean slow to react (also known as Robust)
[Fe((H2O)5F]2+ = labile, but it is very thermodynamically stable
[Co(NH3)6]3+ = inert, but thermodynamically unstable
c) Inert complexes react slowly, so their products can be isolated and studied

d) Inert metal ions = those with large LFSE

i. d3, low spin d4-d6
ii. Low spin d8
e) High spin (weak field) d8 metals are intermediate in lability
B. The Dissociative (D) Substitution Mechanism
1) The mechanism is essentially the same as SN1 in organic chemistry
a) Dissociation of one ligand results in an isolatable intermediate
b) The new ligand binds at the open coordination site
2) The kinetic analysis
a) The Steady State Hypothesis
i. Intermediates are high energy species (5-coord metal ion)
ii. They react almost as soon as they are formed
iii. Their concentrations are small and constant over most of the course of a
reaction
b) The D rate Law
C. The Interchange (I) Substitution Mechanism
1) The mechanism involves the incoming ligand (Y) in the rate determining step
a) Y can weakly assist the leaving ligand (X) = Dissociative Interchange (ID)
b) Y can strongly begin bond formation before X leaves = Associative
Interchange (IA)

2) The kinetic analysis

a) Assumptions to simplify the analysis
i. [Y] = very large, [Y]0 = [Y]
ii. k2 << k-1 which means reaction #1 is in equilibrium with K1 = k1/k-1
iii. [M]0 = [ML5X] + [ML5X•Y]

b) Steady State Equation

D. Comparison of D and I Rate Laws
1) We can rewrite the I and D rate laws for comparison:

2) If [Y] is small, both become second order expressions

k[M][Y]
a) For D, we get Rate 
[X]
b) For I, we get Rate  k[M]0 [Y]0
 3) If [Y] is large, both become first order expressions k
Rate  [M]0
For both I and D, we get k'
4) These similarities make it difficult to ever tell these two mechanisms apart based
on experimental data
a) Usually, we vary the concentration of [M], [Y], or [X] to find the order
b) Isolation of ML5 is proof of the D mechanism

E. The Associative (A) Substitution Mechanism

1) The mechanism is essentially the SN2 mechanism from Organic chemistry
a) Y and X are both partially bonded to M at the transition state
b) No Intermediate is usually isolated
F. Experimental Evidence for the Octahedral Substitution Mechanism
1) The usual mechanism for Octahedral complexes is Dissociation
2) Even if a reaction is thermodynamically downhill, a large Ea will make it slow
3) Thermodynamically uphill reactions won’t occur even if Ea is small
4) Ligand Field Activation Energy = LFAE = difference in ligand field stabilization
energy between the octahedral complex and the 5-coordinate intermediate
supports the assignment of labile and inert metal ions

3) Oxidation State: higher charge = slower reaction due to greater ligand attraction
4) Ionic Radius: smaller ionic radius = slower reaction due to greater ligand
attraction
5) Other Evidence for Dissociative Mechanism
a) Incoming ligand identity has no effect on rate
b) Bulky X increases the rate
c) DVa = volume of activation is positive for octahedral substitutions because
one molecule splits into two at the intermediate
G. The Associative Substitution Mechanism and Octahedral Complexes
1) This mechanism is sometimes observed, but is rare
2) If the identity of Y influences the rate, that suggests Association
3) If DSa is negative (molecules coming together), that suggests Association
H. The Conjugate Base Mechanism (SN1CB) of Substitution
1) This mechanism requires a deprotonatable ligand on the complex (NH3, H2O)
2) It also requires presence of hydroxide OH- in aqueous solutions
3) Mechanism:

4) Deprotonation lowers the charge on the complex ion, so X- leaving is easier

5) Evidence
a) H exchange on ammonia ligands is well known
b) RNH2 is faster than NH3, because steric crowding favors dissociation
c) R3N ligands completely stop the reaction (no ionizable protons)
6) The position trans to X is usually the one deprotonated. The trigonal bipyramidal
intermediate is more easily achieved.
Bonding and Structure in Transition Metal Complexes

Organo-transition metal catalyzed reactions are treated as

sequences of elementary
reactions.

Knowledge of tm-complex
structure is therefore important
to the study of catalytic
processes.

We will examine:
1. Ligand bonding modes
2. Coordination number and geometry
3. Metal oxidation state and effective atomic number of a
complex.