Subject Chemistry

Paper No and Title 3 and Inorganic Chemistry-I (Stereochemistry, Metal-

Ligand Equilibria and Reaction Mechanism of Transition
Metal Complexes)
Module No and Title 24 and Kinetics of octahedral substitution

Module Tag CHE_P3_M24

CHEMISTRY Paper No. 3: Inorganic Chemistry-I (Stereochemistry, Metal-

Ligand Equilibria and Reaction Mechanism of Transition
Metal Complexes)
Module No. 24: kinetics of octahedral substitution
 TABLE OF CONTENTS

1. Learning Outcomes
2. Kinetics of octahedral substitution
2.1 Dissociative Nucleophilic Substitution Reaction
2.2 Associative Nucleophilic Substitution Reaction
2.3 Interchange mechanism
3. Exchange reaction
4. Substitution reactions of octahedral complexes

5. Summary

CHEMISTRY Paper No. 3: Inorganic Chemistry-I (Stereochemistry, Metal-

Ligand Equilibria and Reaction Mechanism of Transition
Metal Complexes)
Module No. 24: kinetics of octahedral substitution
 1. Learning Outcomes

After studying this module, you shall be able to

• Know the Kinetics of octahedral substitution
• Basics of Substitution reactions of octahedral complexes
• Mechanism involve in the substitution of octahedral complexes
• Rate of exchange of water in the octahedral complexes

2. Kinetics of octahedral substitution

Three types of nucleophilic substitution reaction is known and differentiation among

them is still a big task. These three types are: Dissociative Nucleophilic Substitution,
Associative Nucleophilc Substitution reaction and Interchange reaction
Let’s discuss mechanism and kinetics of each type of the nucleophilic substitution
reaction one by one.
2.1 Dissociative Nucleophilic Substitution Reaction: Dissociative nucleophilic
substitution reaction involves two step processes. In the first step of leaving group breaks
in to form a five coordinated intermediate, which is second step combine with a ligand to
form a six coordinated specie:

Rate of formation of product i.e. d[ML5Y]/dt = k2[ML5].[Y] ………………… (1)

CHEMISTRY Paper No. 3: Inorganic Chemistry-I (Stereochemistry, Metal-

Ligand Equilibria and Reaction Mechanism of Transition
Metal Complexes)
Module No. 24: kinetics of octahedral substitution
 But, concentration of intermediate ML5 is not known at any instance of time. So, its
concentration should be determined in terms of concentration of ML5X and Y. Since,
[ML5] is forming in step 1 and disappearing in step 2. So,
d[ML5]/dt = k1.[ML5X] - k-1.[ML5][X] – k2[ML5].[Y]
So, intermediate ML5 is forming from one side and disappearing from other. So, a
condition will reach where, rate of formation and disappearance of ML5would become
equal. This state is called steady state approximation. So, applying,steady state
approximation,
d[ML5]/dt = k1.[ML5X] - k-1.[ML5][X] – k2[ML5].[Y] = 0
or, k-1.[ML5][X] + k2[ML5].[Y] = k1.[ML5X]
[ML5].{k-1[X] + K2.[Y]} = k1.[ML5X]
Therefore, [ML5] = k1.[ML5X]/{k-1[X] + K2.[Y]} -------------------------- (2)
Putting value of [ML5] in equation 1:
Rate of reaction = d[ML5Y]/dt = k2[ML5].[Y]
= k1.k2.[ML5X].[Y]/{k-1[X] + k2.[Y]} ----------------------------------(3)
Second step in this type of reaction is very fast and therefore, K2.[Y] >> k-1[X]. So. If we
ignore, k-1 in front of k2[Y]. The rate of reaction seems to be,
Rate of reaction = d[ML5Y]/dt = k1.[ML5X] ---------------------------- (4)
2.2 Associative Nucleophilic Substitution Reaction: Associative nucleophilic
substitution reaction is also a two-step process. In step 1, ligand Y associate with [ML5X]
to form a seven coordinated intermediate [ML5XY], which breaks to form [ML5Y] in
subsequent step.

CHEMISTRY Paper No. 3: Inorganic Chemistry-I (Stereochemistry, Metal-

Ligand Equilibria and Reaction Mechanism of Transition
Metal Complexes)
Module No. 24: kinetics of octahedral substitution
 Rate of formation of product i.e. d[ML5Y]/dt = k2[ML5XY] ………………… (5)
Since, [ML5XY] is forming in step 1 and disappearing in step 2. So, rate of formation of
[ML5XY] will be,
d[ML5XY]/dt = k1.[ML5X].[Y] - k-1.[ML5XY] – k2[ML5XY]
Applying steady state approximation,
k1. [ML5X].[Y] - k-1.[ML5XY] – k2[ML5XY] = 0
or, [ML5XY] = k1.[ML5X].[Y]/(k-1 + k2) -------------------------- (6)
Putting this value in equation 4:
d[ML5Y]/dt = k2.k1[ML5X].[Y]/(k-1 + k2)
or, d[ML5Y]/dt = k.[ML5X].[Y] ------------------------------ (7)
where, k = d[ML5Y]/dt = k2.k1/(k-1 + k2)
So, this reaction is of second order kinetics
2.3 Interchange mechanism: This is a bridging mechanism between SN1 and SN2. In
which attacking ligand Y forms an ion pair with the substrate ML5X, and then leaving
group X breaks to form ML5Y.

CHEMISTRY Paper No. 3: Inorganic Chemistry-I (Stereochemistry, Metal-

Ligand Equilibria and Reaction Mechanism of Transition
Metal Complexes)
Module No. 24: kinetics of octahedral substitution
 Rate of formation of product i.e. d[ML5Y]/dt = k2[ML5X.Y] ………………… (8)
Since, [ML5X.Y] is forming in step 1 and disappearing in step 2. So, rate of formation of
[ML5X.Y] will be,
d[ML5X.Y]/dt = k1.[ML5X].[Y] - k-1.[ML5X.Y] – k2[ML5X.Y] ----------- (9)
Let total concentration of reactant i.e. [M0] = [ML5X] + [ML5X.Y]
So, [ML5X] = [M0] – [ML5X.Y] ---------------------------- (10)
Putting, value of [ML5X] in equation (9)
d[ML5X.Y]/dt = k1.{[M0] – [ML5X.Y]}.[Y] - k-1.[ML5X.Y] – k2[ML5X.Y]
= k1[M0].[Y] – k1.[ML5X.Y].[Y] - k-1.[ML5X.Y] – k2[ML5X.Y]
Or, [ML5X.Y] = k1.[M0].[Y]/ {k1.[Y] + k-1 + k2}
Putting this value in equation 8:
d[ML5Y]/dt = k2.k1.[M0].[Y]/ {k1.[Y] + k-1 + k2}
Dividing both numerator and denominator by the constant k2 and if k1/k2 = k and k-1/k2 =
k’, then
d[ML5Y]/dt = k2.k1.[M0].[Y]/ {k.[Y] + k’ + 1} ------------------------- (11)
If an ion pair is formed, but dissociative mechanism is more favorable, then k2>> k-1 and
because of high concentration of Y at any spot of time in the reaction k[Y] >> 1. As a
result of which reaction will seem to follow first order kinetics. Such reaction mechanism
is Dissociative interchange and represented by Id. Similarly, if reaction is bent towards
SN2 reaction then concentration of Y will not as much high as it can be ignored in front

CHEMISTRY Paper No. 3: Inorganic Chemistry-I (Stereochemistry, Metal-

Ligand Equilibria and Reaction Mechanism of Transition
Metal Complexes)
Module No. 24: kinetics of octahedral substitution
 of other constants of equation 11. In such cases, reaction will seem to be tilted towards
SN2 mechanism. Please remember all these formula obtained for different nucleophilic
substitution reaction, which we will use later in this module.

3. Exchange reaction

In all above cases of nucleophilic substitution reaction if X and Y become identical, then
the type of substitution reaction performed is called an Exchange reaction. For example,

If one can scan the rate of hydrolysis of various octahedral metal complexes, the various
complexes can be divided in the fallowing categories.
Category I: the rate of exchange of coordinated water is very fast (~108s-1). The case is
generally found in group 1st (Alkali metals) – on stepping down the group the size of
cations increases, consequently the charge density decreases so the Mn+-OH2 bond
strength decreases, hence bonds are easily broken. For group 2nd (Alkaline earth metals) –
the charge density is larger, hence the strength of the Mn+-OH2 bond is comparatively
greater and rate of exchange is slower.
Category II: the rate of exchange of coordinated water is fast (105 - 108s-1).
Category III: the rate of exchange of coordinated water is slower (1 – 104s-1).
These two categories included Be2+, Al3+, V2+, most of the first row transition metal ions
and the lanthanides metal ions. For transition metal ions the substitution rates decrease
across the series for exampleMn2+> Fe2+> Co2+. This is because of the increase in
effective nuclear charge (Zeff) on moving from left to right in the series and also the
crystal field activation Energy (CFAE) affects the rates of exchange here.

CHEMISTRY Paper No. 3: Inorganic Chemistry-I (Stereochemistry, Metal-

Ligand Equilibria and Reaction Mechanism of Transition
Metal Complexes)
Module No. 24: kinetics of octahedral substitution
 Category IV: the rate of exchange of coordinated water is very slow (10-3 - 10-6s-1).
These are chemically inert complexes. This category includes Cr3+, Co3+, Rh3+, Ir3+, Pt2+
ions. The rate of exchange of water is depending on the size of the cations as well as on
CFSE. The d3 and d6 ions are almost inert for example Rh3+ (low spin d5), Cr3+ (d3) and
Co2+ (d6). To trace the reason for such reaction students can direct themselves to the
module, where we have discussed about crystal field approach of labile and inert
complexes for the formation of higher coordinated intermediate.

4. Substitution of octahedral complexes

In most of the substitution reaction, solvent interfere nucleophilic substitution reaction
i.e. before attack of nucleophile, solvent replace the leaving group and form a different
complex, which not only effect mechanism of the reaction, but also provide wrong
information about kinetics of the reaction. The kinetic studies on the substitution reaction
of octahedral complex have been studies in aqueous medium. Rate of substitution
reactions in aqueous solution can be effected by the presence of acid or base in the
medium.

The pH of the Solution is the deciding factor for nature of the product in the hydrolysis
reactions; the water containing complex is obtained in acidic solution while the hydroxo

CHEMISTRY Paper No. 3: Inorganic Chemistry-I (Stereochemistry, Metal-

Ligand Equilibria and Reaction Mechanism of Transition
Metal Complexes)
Module No. 24: kinetics of octahedral substitution
 (HO-) complex is obtained in basic Solution. Now, if you will apply formula for rate of
reaction for both SN1 or SN2 type reaction, the rate would be,
Rate of reaction = -d[Cu(NH3)5Cl]/dt = k1.[Cu(NH3)5Cl] in case of SN1 reaction and
-d[Cu(NH3)5Cl]/dt = k.[Cu(NH3)5Cl]2+.[H2O] in case of SN1 reaction. Since,
concentration of water is large enough and therefore practically no change in the
concentration of water will be obtained. So, kinetic study in case of acid or base
hydrolysis will always misguide about the reaction mechanism.
The rate constant for hydrolysis of [Co(NH3)5Cl]2+ is basic solution is a million
times faster than acidic solution i.e. kB is about 104 to 108 times higher than kA.
We will learn acid and base hydrolysis in the next module.

5. Summary

 Nucleophilic substitution reaction have two extremes: in one extreme, leaving

group break first from an octahedral substrate and then nucleophile attack on the
five coordinated intermediate. This is called dissociative Nucleophilic
Substitution reaction. While, if attacking ligand join the substrate to form a seven
coordinated intermediate, then the reaction is called associative nucleophilic
substitution reaction.
 Dissociative nucleophilic substitution reaction follow first order kinetics, while
associative nucleophilic substitution reaction shows second order kinetics.
 An interchange reaction shows intermediate behavior of two extremes, in which
an ion pair forms before reaction follow SN1 or SN2 reaction. The interchange
reaction can show nearby mechanism of dissociative reaction and interchange
reaction in such case is called dissociative interchange reaction. If interchange

CHEMISTRY Paper No. 3: Inorganic Chemistry-I (Stereochemistry, Metal-

Ligand Equilibria and Reaction Mechanism of Transition
Metal Complexes)
Module No. 24: kinetics of octahedral substitution
 reaction shows mechanism that seems to be nearby SN2 reaction, then the reaction
is called Associative interchange reaction.
 If leaving group and attacking lignds are same, then the reaction is called an
exchange reaction. For exchange of water following trend was observed:

 Kinetic study of acid or base hydrolysis provides misinterpretation about the

mechanism of the reaction.

CHEMISTRY Paper No. 3: Inorganic Chemistry-I (Stereochemistry, Metal-

Ligand Equilibria and Reaction Mechanism of Transition
Metal Complexes)
Module No. 24: kinetics of octahedral substitution