CHELATE EFFECT

CHELATES:

 A Compound containing a ligand bonded to a central metal atom at two or more points.

 A chelaing ligand is biendendate or polydendate ligand which is attached to the same

central metal atom by two or more of its donor atoms resulting in the formation of a
complex having a strain- free ring strucure.

 The complex having the ring structure is called chelate or chelated complex.

 The chelate is also called by various other names like cyclic complex,ring- type
complex etc.

 The formation of a chelate is called chelation or cyclisation.

CHELATE EFFECTS

 The enhanced stability of a complex system containing chelate ring as

compared to the stability of a system that is as similiar as possible but
contain none or fewer rings.
 The stability of the complex of a metal ion with a bidentate ligand such as en is
significantly greater than the complex of the same ion with two monodentate
ligands of comparable donor ability, i.e for example two ammonia molecule.
 For example consider the stability constants for the following complexes.

Ni2+(aq) +6NH3(aq) = [ 𝐍𝐢(𝐍𝐇 𝟑)𝟔 ] 𝟐+¿   l

Ni2+ (aq)+ 3en(aq) = [ 𝐍𝐢𝐞𝐧𝟑 ] 2+¿  l=18.28

 

 The system[ 𝐍𝐢𝐞𝐧𝟑 ] 2+¿ in which three chelate rings are formed is more stable than that in
which no such ring is formed. Although the effect is not always so pronounced, such a chelate
effect is very general one.

 In order to understand the chelate effect properly, we must consider in more detail the
thermodynamic significance of stability constants.
THERMODYNAMIC ORIGIN OF CHELATE EFFECT

• Stability
   of chelates can be explained on the basis of standard free energy change() and
the standard entropy change().

OR =-RT ln

 The principal driving force for the chelation phenomena is the stability gain arising from the
increasing entropy during the complexation.

 As the enthalpy chang between non-chelate and chelate is almost negligible because of the
similiar metal-ligand donor type.

 The free energy change is primarily governed by the value of

•  will became more negative with a more positive value of , which in turn would increase the

value of stability constant

 Hence the stabiliy of metal complexes increases with chelation as it occurs through an
increment in entropy of the system.
• A  product will be stable if value of is negative and value of is positive.


 During the formation of a non chelated compound with monodentate ligands, the number of
molecules on both side is equal(5 molecules each side), hence will be zero and the value of will
be negative.

 With bidentate and tridendate ligand , number of product molecule (5molecules)is greater than
the number of reactant molecules (3 and 2).

 Hence entropy of product is greater than reactant and thus , will be positive and value will
became more negative.

 Thus it may be concluded that has more negative value for chelates which are formed by the
reaction of bidendate or other polydendate ligands and therefore, are more stable as compared
to the non chelated compounds.
 The stability of chelated complexes also depends on the size of the ring formed in the
complex.

 It is noticed that there will be a decrease in the magnitude of chelate effect with increasing
ring size.

 when the ring that must be formed becomes sufficiently large (seven membered or more) , it
becomes more probable that the other end of the chelate molecule will contact another metal
ion than that it will come around to the first one and complete the ring.
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