Reaction mechanism of Coordination Complexes

Complexes are classified as Inert and Labile ( kinetic stability) depending on

their reactivity.

According to Henry Taube, a Nobel Laureate, the definition is

 If the half life period of 0.1 M solution at RT is less than 1 min. ( t½ < 1
min) the complex is called Labile

 If the half life period of 0.1 M solution at RT is more than 1 min. ( t½ > 1
min) the complex is called Inert

SUBSTITUTION REACTIONS IN COMPLEXES

Complexes usually undergo substitution reactions by the replacement of

ligands with others.

The reaction is common in Octahedral and Square planar complexes and

follows two different paths SN1 and SN2

I.Dissociation Mechanism (SN1 )

Step (i) Slow step : dissociation of ligand (Y)

MX5Y  MX5 + Y
( CN = 6 ) ( CN = 5 )
Octahedral Trigonal bipyramidal

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Step (ii) Fast step : Addition of new ligand (Z)

MX5  MX5 Z
( CN = 5 ) ( CN = 6 )
Trigonal bipyramidal Octahedral

Mechanism :

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II. Association Mechanism (SN2 )

Step (i) Slow step : Association of ligand (Z) to complex

MX5Y + Z  MX5 YZ
( CN = 6 ) ( CN = 7 )
Octahedral Pentagonal bipyramidal

Step (ii) Fast step : Leaving the ligand (Y)

MX5 YZ  MX5 Z
( CN = 7 ) ( CN = 6 )
Pentagonal bipyramidal Octahedral

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 Substitution reactions in Square Planar
complexes
Association mechanism is favorable in square planar complexes

Association Mechanism (SN2 )

Step (i) Slow step : Association of ligand (Z) to complex

MX3Y + Z  MX3 YZ
( CN = 4 ) ( CN = 5 )
Square planar Trigonal bipyramidal

Step (ii) Fast step : Leaving the ligand (Y)

MX3 YZ  MX3 Z
( CN = 5 ) ( CN = 4 )
Trigonal bipyramidal Square planar

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 Trigonal bipyramidal

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 TRANS EFFECT
It is observed that during the substitution reactions of square planar metal
complexes, some ligands preferentially direct the substitution trans to
themselves. i.e., the choice of leaving group is determined by the nature of
ligand trans to it.

The Trans effect can be defined as the effect of a ligand over rate of
substitution of another ligand positioned trans to it in the square planar
complexes.

The ability of a ligand to direct the incoming group to the position trans to it,
is called trans directing effect

The rough order of trans-directing effect of various ligands is:

NO+, CO, CN-, C2H4 > PR3, H- > Me- > Ph- > NO2-, I-, SCN- > Br- > Cl- >

Py, NH3, OH-, H2O

Ex 1:

In the second step, the trans-directing effect of Cl- > NH3

therefore cis-isomer is formed
Ex 2:

In the second step, the trans-directing effect of Cl- > NH3

therefore trans-isomer is formed

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Explanation :

Ex 3: synthesis of cis and trans – [Pt (NH3)(NO2)Cl2]

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