THERMODYNAMIC &

KINETIC ASPECTS OF
METAL COMPLEXES

Inorganic Chemistry
B.Sc. III

Presentation By:
Sitanshu Kumar
 STABILITY
• Discussed under two main types:-

1. Thermodynamic Stability
2. Kinetic Stability

Generally we talk about

THERMODYNAMIC STABILITY,
unless KINETIC or RATE OF
FORMATION word is mentioned.
 POINTS OF DIFFERENCE
 Thermodynamic Stability
Relates to the time period of
existence of a species in a particular form.

 Kinetic Stability
Refers to the faster rate of formation of the
particular species.
 STABILITY CONSTANTS
 Higher the value of equilibrium constant for a
reaction, more stable is the product formed.

 TYPES:
1. Stepwise stability constant
2. Overall stability constant
FORMATION OF MLn COMPLEX
 Two different ways:
1. Stepwise formation

M + L------> ML ; K1 = [ML]/[M][L]

ML + L ----> ML2 ; K2 = [ML2]/[ML][L]

.
.
MLn-1 + L -----> MLn ; Kn = [MLn]/ [MLn-1][L]

 K1, K2, Kn are known as stepwise stability constants.

2. Overall formation:
M + L------> ML ; β1 = [ML]/[M][L]

M + 2L ----> ML2 ; β2 = [ML2]/[M][L]2

.
.
M + nL -----> MLn ; βn = [MLn]/[M][L]n

 β1, β2, βn are known as overall stability

constants.
 Proceeding with rate constants, we get,

β1 = K1
β2 = K1 . K2
βn = K1 . K2 . K3 ………. Kn

Taking log, we get,

log βn = log K1 + log K2 + log K3 +……. log Kn.

 Complex is stable if log β >= 8.

INERTNESS & LABILITY OF COMPLEXES

 Lability refers to reactivity and Inertness refers

to non- reactivity of the complex.
 In other words, complex with ability to
exchange its ligand(s) present inside co-
ordination sphere is labile otherwise inert.
 Inert complexes have substitution reaction half
life period larger than a minute & opposite for
labile complexes.
 FACTORS AFFECTING STABILITY OF
COMPLEXES

1. Nature of Metal Ion:

 +ve Charge on metal ion ↑, stability of complex↑

 Size of metal ion ↓, stability of complex ↑

 Charge:size ratio ↑, stability of complex ↑

 more electronegative metal ions form complexes with

ligand having donor atom of high electronegativity &
vice versa.
2. Nature of ligand:

 -ve charge on ligand ↑, stability of complex ↑

 Size of ligand ↓, stability of complex ↑
 Basic strength of ligand ↑, stability of complex↑
 Presence of chelating ligand makes the
complex more stable.
 Ligand bulkiness↓ , stability of complex↑,
because of less stearic hindrance.
SUBSTITUTION REACTIONS IN
SQUARE PLANAR COMPLEXES
• 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
 TRANS EFFECT
 Definition
The trans effect is best defined as the effect of a
coordinated ligand upon the
rate of substitution of ligands opposite to it.
Or
The ability of a ligand in a square planar complex to
direct the replacement if the ligand trans to it.

The trans effect is given as the following series:

CN- > NO2- > I- = SCN- > Br- > Cl- > py > NH3 > H2O
Substitution reactions in square-planar complexes
the trans effect

L X L Y
+X, -Y
M M
T L T L
In the above reaction, “T” is the ligand having good trans
effect ; L’s are the inert ligands & “X” is the labile ligand.
MECHANISM OF Nu- SUBSTITUTION REACTION

L L S
M +S
L X L L
M
+Y L X

-X
Y
L L L L
M M
L X L S
+Y

Y
L L
-X M
L S
L L
M -S
L Y
THEORIES EXPLAINING TRANS EFFECT (∏-bonding)

 p-backbonding to a
metal is weakened
when it is trans to
another good
p-backbonding ligand.

 p-backbonding to a
metal is strengthened
when it is trans to a
good s-donating ligand
that can’t p-backbond .
Polarization theory:-

This theory explains the weakening of metal-leaving

group bond due to the more polarizable nature of
Trans ligand, resulting in cleavage of the former bond
and thus SUBSTITUTION.

∂+ T ∂- ∂+ M ∂- X

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