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Reaction Mechanism of Coordination Complexes

Coordination complexes can undergo substitution reactions through either SN1 or SN2 mechanisms. In the SN1 mechanism, ligand dissociation is the slow step followed by rapid addition of a new ligand. In the SN2 mechanism, association of the new ligand is the slow step followed by departure of the original ligand. Square planar complexes favor the SN2 mechanism, with association of the new ligand forming a pentagonal bipyramidal intermediate. The trans effect describes how some ligands in square planar complexes preferentially direct substitution to occur trans to their position, with ligands like NO+ and CO exhibiting a strong trans directing ability.

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1K views7 pages

Reaction Mechanism of Coordination Complexes

Coordination complexes can undergo substitution reactions through either SN1 or SN2 mechanisms. In the SN1 mechanism, ligand dissociation is the slow step followed by rapid addition of a new ligand. In the SN2 mechanism, association of the new ligand is the slow step followed by departure of the original ligand. Square planar complexes favor the SN2 mechanism, with association of the new ligand forming a pentagonal bipyramidal intermediate. The trans effect describes how some ligands in square planar complexes preferentially direct substitution to occur trans to their position, with ligands like NO+ and CO exhibiting a strong trans directing ability.

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MartinMagu
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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

srrchemistrylessons 1
Step (ii) Fast step : Addition of new ligand (Z)

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

Mechanism :

srrchemistrylessons 2
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

srrchemistrylessons 3
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

srrchemistrylessons 4
Trigonal bipyramidal

srrchemistrylessons 5
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

srrchemistrylessons 6
Explanation :

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

srrchemistrylessons 7

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