COORDINATION CHEMISTRY

Coordination Chemistry
The thermodynamics of complex formation:
Formation constants
A formation constant expresses the interaction strength of a ligand
relative to the interaction strength of the solvent molecules (usually H2O)
as a ligand

[H2O] = 1

The value of Kf indicates the strength of binding of the ligand

relative to H2O: if Kf is large, the incoming ligand binds more strongly
than the solvent, H2O; if Kf is small, the incoming ligand binds more
weakly than H2O
 Coordination Chemistry
The thermodynamics of complex formation:
Formation constants
A formation constant expresses the interaction strength of a ligand
relative to the interaction strength of the solvent molecules (usually H2O)
as a ligand

Kf constants for the reaction [M(H2O)n]m+ + L ⇌ [M(L)(OH2)n-1]m+ + H2O

 Coordination Chemistry
The thermodynamics of complex formation:
Formation constants
The discussion of stabilities is more involved when more than one ligand
may be replaced. For instance, in the reaction of [Ni(OH2)6]2+ to give
[Ni(NH3)6]2+

If the overall reaction is M + nL ➝ MLn, the stepwise formation

constants are
 Coordination Chemistry
The thermodynamics of complex formation:
Formation constants
The discussion of stabilities is more involved when more than one ligand
may be replaced. For instance, in the reaction of [Ni(OH2)6]2+ to give
[Ni(NH3)6]2+

In general, we have:
[KLn ]
Kfn =
[KLn −1][L]

The overall formation constant, β

! n:
 Coordination Chemistry
The thermodynamics of complex formation:
Trends in successive formation constants
Stepwise formation constants typically lie in the order Kfn > Kfn+1, as
expected statistically; deviations from this order indicate a major change in
structure

The magnitude of the formation constant is a direct reflection of the

sign and magnitude of the standard Gibbs energy of formation
(because ΔrG o = −RT ln Kfn
Kf1 > Kf2 > ... > Kfn
This general trend can be explained quite simply by considering the
decrease in the number of the ligand H2O molecules available for
replacement in the formation step, as in

.. compared with
 Coordination Chemistry
The thermodynamics of complex formation:
Trends in successive formation constants
Stepwise formation constants typically lie in the order Kfn > Kfn+1, as
expected statistically; deviations from this order indicate a major change in
structure: Kf1 > Kf2 > ... > Kfn

Formation constants of Ni(II) ammines, [Ni(NH3)n(OH2)6-n]2+

 Coordination Chemistry
The thermodynamics of complex formation:
Trends in successive formation constants
A reversal of the relation Kfn > Kfn+1 is usually an indication of a major
change in the electronic structure of the complex as more ligands are
added

The complex [Fe(bpy)3]2 is strikingly stable compared with the bis

complex, [Fe(bpy)2(OH2)2]2+

[Fe(bpy)2(OH2)2]2+ [Fe(bpy)3
high-spin (weak-field) low-spin (strong-field)
4 2 6
!t2g eg configuration !t2g configuration

There is a considerable increase in the LFSE

 Coordination Chemistry
The thermodynamics of complex formation:
Trends in successive formation constants
A contrasting example is the halogeno complexes of Hg(II), where Kf3 is
anomalously low compared with Kf2:

The decrease between the second and third values is too large
to be explained statistically and suggests a major change in the
nature of the complex, such as the onset of four-coordination:
 Coordination Chemistry
Excercise
Interpreting irregular successive formation constants
The successive formation constants for complexes of cadmium with Br are
Kf1 = 36.3, Kf2 = 3.47, Kf3 = 1.15, Kf4 = 2.34. Suggest an explanation of
why Kf4 > Kf3
 Coordination Chemistry
Excercise
Interpreting irregular successive formation constants
The successive formation constants for complexes of cadmium with Br are
Kf1 = 36.3, Kf2 = 3.47, Kf3 = 1.15, Kf4 = 2.34. Suggest an explanation of
why Kf4 > Kf3

The anomaly suggests a structural change. Aqua complexes are usually

six-coordinate whereas halogeno complexes of M2+ ions are commonly
tetrahedral. The reaction of the complex with three Br- groups to add
the fourth is

[CdBr3(OH2)3]-(aq) + Br(aq) ➝ [CdBr4]2-(aq) + 3H2O(l)

This step is favoured by the release of three H2O molecules

from the relatively restricted coordination sphere environment.
The result is an increase in Kf
 Coordination Chemistry
The chelate and macrocyclic effects
The chelate and macrocyclic effects are the greater stability of
complexes containing coordinated polydentate ligands compared with a
complex containing the equivalent number of analogous monodentate
ligands

When Kf1 for the formation of a complex with a bidentate

chelate ligand, such as ethylenediamine (en), is compared with
the value of β
! 2 for the corresponding bis(ammine) complex, it is
found that the former is generally larger
 Coordination Chemistry
The chelate and macrocyclic effects
The chelate effect can be traced primarily to differences in reaction
entropy between chelated and non-chelated complexes in dilute solutions

M o r e + ΔS
! implies
2 molecules 3 molecules
more favorable process

3 molecules 3 molecules

The chelation reaction results in an increase in the number of

independent molecules in solution. By contrast, the nonchelating
reaction produces no net change
 Coordination Chemistry
The chelate and macrocyclic effects
The macrocyclic effect is thought to be a combination of the entropic
effect seen in the chelate effect, together with an additional energetic
contribution that comes from the preorganized nature of the ligating
groups

In macrocyclic ligands, where multiple donor

atoms are held in a cyclic array, such as
crown ethers or phthalocyanin, give complexes
of even greater stability than might otherwise
be expected

A formation constant of 10 12 to 10 25 is
generally associated with a chelate or
macrocyclic effect

The majority of reagents used in complexometric titrations in

analytical chemistry are polydentate chelates like edta4, and most
biochemical metal binding sites are chelating or macrocylic ligands
 Coordination Chemistry
Steric effects and electron delocalization
The stability of chelate complexes of d metals involving diimine ligands is
a result of the chelate effect in conjunction with the ability of the ligands
to act as π acceptors as well as !σ donors

diimine bipyridine phenanthroline

They form five-membered rings with the metal atom

Complexes containing chelating ligands with delocalized electronic

structures may be stabilized by electronic effects in addition to the
entropy advantages of chelation
 Coordination Chemistry
Steric effects and electron delocalization
The great stability of their complexes with d metals is probably a result of their
ability to act as π
! acceptors as well as donors and to form π
! bonds by
overlap of the full metal d orbitals and the empty ring π*
! orbitals

[Ru(bpy)3]2

This bond formation is favoured by electron population in the metal t2g

orbitals, which allows the metal atom to act as a π
! donor and transfer
electron density to the ligand rings. An example is the complex
[Ru(bpy)3]2
 Coordination Chemistry
Steric effects and electron delocalization
The reaction shown above is an example of a condensation reaction, a
reaction in which a bond is formed between two molecules, and a small
molecule

One molecule of H2O is eliminated

If the metal ion had not been present, the condensation reaction of the
component ligands would have been an ill-defined polymeric mixture. The
metal can be removed to leave the multi dentate ligand intact
 Coordination Chemistry
Steric effects and electron delocalization
This phenomenon, which is called the template effect, can be applied to
produce a surprising variety of macrocyclic ligands