Substitution reactions

• Electrophilic substitution reactions

• Nucleophilic substitution reactions

•Nucleophilic substitution reactions
*acid hydrolysis
*base hydrolysis
*anation
*ligand exchange etc…
Mechanisms of substitution:
• Associative mechanism(A)
• Dissociative mechanism(D)
• Interchange mechanism(I)
* Interchange Associative(Ia)
* Interchange Dissociative(Id)
 slow +Y(fast)

Associative : [L5MX] [L5M] [L5MY]

5-coordinate complex

slow X -X(fast)

Dissociative : [L5MX]+Y [L5M ] [L5MY] + X

Y
7-coordinate complex

slow X -X(fast)

Interchange : [L5MX]+Y [L5M ] [L5MY] + X

Y
7-coordinate transition state
Note :
There will be some cases in which it is difficult to find which
mechanism is followed to give the product i.e., in cases when there is
* solvent interaction
*ion pair interaction etc…
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 DEFINITIONS

The ability of a complex to engage in reaction that results in

replacing one or more ligands in it’s coordination sphere
(by other ligands) is called lability and the complexes in which the
ligands are rapidly replaced by others are called labile complexes.

The inability of a complex to engage in such reaction is termed

as inertness and the complexes which exhibit such property are
called labile complexes.
> H.TAUBE has described the complexes as labile if they have
half life(t1/2) of reaction under 30 sec while the reactions having
half life greater than 30 sec are termed as inert.

t1/2 < 30 sec LABILE complex

t1/2 >= 30 sec INERT complex
The terms inert and labile are kinetic terms because they reflect the rate with
which the reaction proceeds and these kinetic terms should not be confused
With thermodynamic terms stable and unstable which refer to tendency of
species to exist(governed by equilibrium constants.)

Consider the reaction: M + nL ⇌ MLn ; βn =[MLn]/[M][L]n

where βn is formation constant of the complex.
The higher values of βn indicate it’s higher thermodynamic stability of the
complex. Thus it gives measure of the extent to which the reaction proceeds
but it cannot say anything about the speed with which equilibrium is attained.
Examples:

* [Hg(CN)4]-2 + 4 14CN- ⇌ [Hg14(CN)4]-2 + 4CN- Thermodynamically

Stable and kinetically
Unstable
log βn =42 ; t1/2= very small

*[Cr(CN)6]-3 + 6 14CN- ⇌ [Cr14(CN)6]-3 + 6 CN- Thermodynamically

Stable and kinetically
stable
log βn =37 ; t1/2= 24 days
* The inertness or lability depends upon the activation energy i.e., high
Activation energy imparts inertness while low activation energy
imparts lability.Thus inertness or lability is determined by ∆G‡
(free energy of activation).
∆G‡ = ∆H‡ - T ∆S‡
The stability of a complex is determined by free energy change(∆G0)in a
reaction.
∆G0 = ∆H0- T ∆S0
• ∆G‡ depends on reaction pathway while ∆G0 depends upon the difference
in free energy of reactants and products.
 VBT interpretation of lability and
inertness in octahedral complexes :

• Outer and inner orbital complexes and their stability

• Kinetic behavior of outer orbital complexes
• Kinetic behavior of inner orbital complexes
For outer orbital complexes:

d0,d1,d2,d7,d8,d9 highly labile

3
d ,d 4 0 1
less labile than d ,d ,d 2

d5,d6 highly inert

 (n-1)d ns np
[V(NH3)6]+3:
(n-1)d ns np
[MnCl6]-3:
(n-1)d ns np nd
[Co(CN)6]-3:

d2sp3 hybridisation
vacancy for entering nucleophile
Limitations of VBT interpretation
 CFT interpretation of lability and
inertness in octahedral complexes :

CFAE = loss of cfse in forming the activated complex

= cfse of the starting complex – cfse of the activated complex

cfse of activated complex ???

 Generalisations:
• Both the high spin and low spin complexes of d0,d1,d2,d7,d9,d10 and
high spin complexes of d4,d5,d6 are generally labile.
• Both high spin and low spin complexes of d3,d8 and low spin
complexes of d4,d5,d6 are generally inert.
Limitations of CFT interpretation

.
INTERESTING MECHANISM
Substitution in square planar complexes is
governed by TRANS EFFECT

TRANS EFFECT???
4 days
TRANS EFFECT
BY
References:

CSIR MATERIAL-
INORGANIC
CHEMISTRY
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