THERMODYNAMIC &

KINETIC ASPECTS OF METAL COMPLEXES

 INERTNESS and LABILITY OF COMPLEXES
We use terms to describe the Thermodynamic and Kinetic aspects of reactivity.
Thermodynamic. Stable or Unstable

Kinetic. Inert or Labile

An inert compound is not “inert” in the usual sense that no reaction will occur.
Rather, the reaction takes place slower than for labile compounds.

There is NO connection between Thermodynamic Stability/Instability

of a complex and its Lability/Inertness toward substitution.

For example:
Stable …but labile

[Ni(CN)4]2- + 413CN- [Ni(13CN)4]2- + 4CN- t1/2 ~ 30sec.

[Ni(CN)4]2- Ni2+(aq) + 4CN-(aq) Keq = 1 x 10-30

Unstable but inert

[Co(NH3)6]3+ + 6H2O [Co(OH2)6]3++ 6NH4+ t1/2 ~ days. Keq = 1 x 1025
 INERTNESS and LABILITY OF COMPLEXES

Lability refers to reactivity and

Inertness refers to non- reactivity of the complex.

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.
 Labile or inert?
L
L L
M
L L

Ea L
L L
L M
L L L L
M X
L L
X
G
 STABILITY

1. Thermodynamic Stability
2. Kinetic Stability

Generally we talk about THERMODYNAMIC STABILITY,

unless KINETIC or RATE OF FORMATION word is mentioned.
 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.
Formation of complexes: Thermodynamics
Orbital occupation effects
 Orbital occupation effects

Dq was derived for quantum mechanic description of the electrostatic model of crystalline fields and is connected
to the radial electron density of the d-electrons, the charge of the metal and the distance of ligands and metal.
The term Dq is the product of two terms D and q and is called Differential of quanta implying the energy. The word
D has been coined from D State (L=2 )
Orbital occupation effects
 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.

Examples of stability constants
Examples of stability constants
Examples of stability constants
FACTORS AFFECTING STABILITY OF COMPLEXES
1. Nature of Metal Ions:

Positive 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 ligands:

Negative 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 steric hindrance.
Factors affecting stability of metal complexes
HSAB
HSAB
The chelate effect
 The chelate effect

• The “chelate effect” is amplified for ligands capable of forming multiple chelate rings
 The macrocyclic effect
The there is a distinct difference between chelating ligands and
macrocyclic ones “macrocyclic effect”
The macrocyclic effect
The macrocyclic effect