I MSC COORDINATION CHEMISTRY UNIT-II

CHELATE EFFECT
Definition

 An equilibrium reaction between the complexing agent and a metal ion.

 The formation of two or more bonds between metal and the complexing agent
are by characterized suitable analytical technique
 Resulting in the formation of a ring structure including the metal ion.
 The term 'chelates was first proposed by Morgan and Drew in 1920 for the cyclic
structure arising from the assembly of metals with organic ligands.
 The chelate effect results in the enhanced affinity of chelating ligands for a metal
ion compared to the affinity of a collection of similar non-chelating monodentate
ligands for the same metal.

Structure of Popular chelating ligands

Ethylenediamine Glycinato
(symmetrical) (unsymmetrical

Characteristic Features of Chelates

 The Chelate complexes generally have low melting points and are soluble in the
organic solvents
 Two characteristic features of the chelate complexes are given as follows
1. Ligand-type
2. Stability
Ligand-type
 Only polydentate ligands are capable of forming chelate complexes.
 The ligand can be bidentate, tridentate or even hexadentate, but it must have
more than one donor sites to form the chelate.
Structure of chelate complexes Co2+ with bidentate ligands

P.RAM KUMAR ASST PROFESSOR OF CHEMISTRY VOC COLLEGE

I MSC COORDINATION CHEMISTRY UNIT-II

Structure of chelate complexes Co2+ with Tridentate ligands

Structure of chelate complexes Ni2+ with Tetradentate ligands

Structure of chelate complexes Ni2+ with pentadentate ligands

Structure of chelate complexes Ni2+ with hexadentate ligands

2.Stability
 The chelating agent binds with the metal cuter of suitable size inflexibly and the
bond can be covalent or coordinate.

P.RAM KUMAR ASST PROFESSOR OF CHEMISTRY VOC COLLEGE

I MSC COORDINATION CHEMISTRY UNIT-II

 This makes the chelate complexes as more stable than their non-chelating
counterparts.
 Five and six-membered ring chelate complexes are more stable than 4,7,8
membered ring due less steric strain.

 The chelating ligands like ethylenediamine which do not have multiple bonds,
prefer to form five-membered rings complexes; while the chelating ligands like
acetylacetonate, which do have double bonds prefer form six-membered rings
complexes.

 The structures of bivalent iron complexes with chelating ligand

Normal 2.2-bipyridyl - less steric hindrance – more stable
4,4-Dimethyl-2-2 bipyridyl - more steric hindrance – less stable

P.RAM KUMAR ASST PROFESSOR OF CHEMISTRY VOC COLLEGE

I MSC COORDINATION CHEMISTRY UNIT-II

Thermodynamic Explanation of Chelation

 The principal driving force for the chelation phenomena is the stability gain
arising from the increasing entropy during the complexation.
 The free energy change for a general reaction is given by
G0 = H0-TS0 [or] G0= -RT ln K--------------[1]
 The enthalpy change between non-chelate and chelates is almost negligible
because of the similar metal-ligand donor type, the free energy change is
primarily governed by the value of S0.

[Cd(H2O)4] + 4CH3NH3 [Cd(CH3NH3)4]2+ + 4H2O

[Cd(H2O)4] + 2en [Cd(en)2]2+ + 4H2O

[Cd(H2O)4] + trien [Cd(trien)]2+ + 4H2O

 The equation [1] that G0 will become more negative with a more positive value of
S0 which in turn would increase the value of stability constant K.
 The stability of metal complexes increases with chelation as it occurs through an
increment in the entropy of the system.
 Chelation is thermodynamic process, as the number species in the product more
than that of the reactant leading to enhanced stability.
 Entropy increases in the cases of trien is higher than ethylenediamine making
the trien chelate complex as more stable
 The stability of chelate complex increases with the denticity of the chelating
agent

Factors affecting stability of chelate complexes

1. Size of chelate ring

 Five and six-membered ring chelate complexes are more stable than 4, 7
and 8 membered ring due less steric strain.
 Stability order of Cu2+ with chelate ligand

P.RAM KUMAR ASST PROFESSOR OF CHEMISTRY VOC COLLEGE

I MSC COORDINATION CHEMISTRY UNIT-II

2. Number of chelate ring and nature of metal ion

 Number of donor sites increases stability of metal chelate increases
 Stability of chelate complexes was also found in accordance with the
Irving Williams series
 Pd > Cu > Ni > Co > Zn > Cd > Fe > Mn > Mg
3. Resonance effect
 Resonance stabilization of chelate ring enhance complex stability
 Exceptionally high log β value [Fe(acac)3] indicates complex will be more
stable due to Resonance stabilization

4. Lewis base strength and charge of the ligand

 Calvin and Wilson studied the Cu2+ chelate complexes proved that the
stability of the chelate complexes increases with the increase of the banc
character of the ligand.
 The uncharged ligands like ethylenediamine triethylenetetraamine form
more stable complexes than the anionic ligands like oxalato or glycinato

P.RAM KUMAR ASST PROFESSOR OF CHEMISTRY VOC COLLEGE

I MSC COORDINATION CHEMISTRY UNIT-II

5. Steric hindrance and strain due to large ligands

 The chelating ligands with large groups usually form less stable complexes
due to the weakening of the metal and bonding from these steric
hindrances.
 For example, ethylenediamine can form more stable complexes with
bivalent metal ion than N-tetramethylethylenediamine which is due to
greater steric hindrance.

TEMPLATE SYNTHESIS

P.RAM KUMAR ASST PROFESSOR OF CHEMISTRY VOC COLLEGE