Coordination Chemistry IV

Reactions & Mechanisms

I. Background
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 Jorgensen 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 how individual molecules react
b) Evidence either supports a mechanism or rules it out
4) Goal: synthesize the predicted products without any by-product by
choosing the appropriate reaction conditions.
C. Types of Reactions: Substitution, Oxidation/Reduction, Ligand
Reactions
 Transition State : MX + Y → [M--X--Y]‡ → MY + X
intermediate sometimes detectable

Principle of microscopic reversibility

 Understanding Inorganic Reaction Kinetics &
Mechanism
 전이상태 (transition state), 중간체 (intermediate)
: 정류-상태 근사법 (steady-state approximation) –
[intermediate] 너무 낮기 때문에 농도변화 없다는 가정
(transforms into another species as soon as it forms)
 실험적 데이터 : 반응차수(order of each reactant)와 속도상
수(rate constant, temperature dependent) 결정, 활성화
자유 에너지 (free energy of activation), 활성화 enthalpy
및 entropy 결정(by studying a reaction at different
temperatures), volume of activation by examination of
pressure dependence on rates
Kinetic Consequences of Reaction Pathways
(반응경로의 반응속도론적 결과)
Overall Reaction Kinetics

rate = -d[A]/dt
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
Understanding Inorganic Kinetics & Mechanism of
Coordination Complexes
H. Taube (1952) : labile, inert (kinetic)
vs stable, unstable (thermodynamic)

M(n-y)+ + nCN- ↔ [M(CN)n]y- in H2O

Kf = [M(CN)n]y- /[M(n-y)+][CN-]n
complex Kf vs exchange rate (14CN-)
Ni(CN)42- 1030 very fast
Fe(CN)64- 1057 very slow

[Co(NH3)6]3+ + 6H3O+ ↔ [Co(H2O)6]3+ + 6NH4+ (ΔG<0)

thermodynamically unstable Keq 1025 but inert (~days, RT)
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. Strong-field d8 (square planar)
e) Weak field d8 metals are intermediate in lability
 Substitution Reaction
Oh: octahedral
Ligand substitution rxn (Oh) – Bailar, Basolo, Pearson, Langford & Gray :
ML5X + Y  ML5Y + X
chemical rxn where the primary coordination sphere changes

[Fe(H2O)5(SCN)]2+ + H2O ↔ [Fe(H2O)6]3+ + SCN-

[Fe(H2O)5(OH)]2+ + H+ ↔ [Fe(H2O)6]3+
[Fe(H2O)6]3+ + Cl- ↔ [Fe(H2O)5Cl]2+ + H2O
[Fe(H2O)5(SCN)]2+ + F- ↔ [Fe(H2O)5F]2+ + SCN-
 Substitution Rxn : labile & inert compounds

labile rxn: t1/2 < 1 min (25oC)

inert rxn : t1/2 > 1 min (25oC)

반응의 종류 :
- Associative (회합, A)
- Dissociative (해리, D)
- Interchange (교환, I) - no intermediate (중간체 검출이 불가능 할 시
는 A, D 대신에 Id 또는 Ia
Id (dissociative interchange) & Ia (associative interchange)
 Mechanism of Substitution Rxn : MX + Y → [M--X--Y]‡ → MY + X

lim: limited
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 (rarely) intermediate
b) The new ligand binds at the open coordination site

2) The kinetic analysis

a) The Steady State Approximation
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 based on Preassociation Complexes

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 first order in [M] and [Y]

a) For D, we get Rate = k[M][Y]
[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) An Intermediate is only rarely isolated
2) Most reaction best fit between D and A, into the ID and IA mechanisms
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 weakly supports the assignment of labile and inert metal ions

5) Oxidation State: higher charge = slower reaction due to greater ligand attraction
6) Ionic Radius: smaller ionic radius = slower reaction due to greater ligand
attraction
7) Other Evidence for Dissociative Mechanism
a) Incoming ligand identity (Y) 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
LFAE = LFSE(Sq Pyr)– LFSE(Oh)
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 (May look like A mech.)
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.