Coordination Chemistry

By
Dr. Priyaranjan Mohapatra
E-mail: priya_chem@vssut.ac.in
Mob: 9437046418

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 Introduction to Crystal Field Theory
Limitation of Valence Bond theory of Complex compounds
 The basic defects of this theory is that it is mainly focused only on the central
atom and not on the ligands.
Does not say anything about the electronic excited states and energies
associated with them
Fails to predict the number, position and intensities of the band observed in the
electronic spectra of coordination compounds.
 According to VBT, the magnetic moment of a complex is due to the magnetic
field due to the spin of the electrons in the metal on. However the magnetic
moment of a complex is due to both spin motion and orbital motion of the
electrons.
 Does not give satisfactory explanation why some complex of a metal ion are low
spin while other complexes of same metal form high spin complexes.
 No prediction regarding the preference of geometry of the complexes.
 No explanation for the characteristic colour of the complexes.
 Fails to explain the liability and inertness of the complex.
 Relative stabilities of the complexes among the congeners for different oxidation
states.
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Basic features of Crystal Field theory
Proposed by Hans Bethe (1929) and Van Vleck (1935).
Based on the concept that when the negative charges of the incoming ligands (or
the negative ends of dipolar molecules like NH3 and H2O) attract the positively
charged metal ion, there is also repulsive interaction between d electrons present
on the metal ion and the ligands
Salient Feature
Ligands are considered as Point like negative charges , which may be the
negative charge on the ligands or the negative end of the dipoles.
The interactions between metal ion and ligands are treated as purely
electrostatic, no covalent interactions are considered. This again is not true,
some of the observations cannot be explained without invoking covalent
interactions. In isolated gaseous metal ion, all of the five d-orbitals are
degenerate.
The metal electrons are supposed to maintain their wave mechanical identity
The metal-ligand interactions are basically electrostatic which may be of ion-
ion or ion-dipole type.
 In transition metal complexes , the electrostatic effect of the ligands on the
energies of d-orbitals is most important aspect of CFT.
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Effect of Electrostatic field of Ligands on the of Metal orbitals
Effect on Metal S-Orbital: As the s-orbital is spherically symmetrical so it is equally
affected by electrostatic field of the ligands from all direction. So in preesence of
electrostatic field only the energy of S-orbital is changed.
Effect of the spherical electrostatic field of the Ligands: If the electrostatic field is
spherically symmetrical in nature then the energies of metal p ,d and f sets of
orbitals are changed but the degeneracy of the orbitals remain unchanged.
For example let us take the case of d-orbitals

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 Effect of unsymmetrical electrostatic field of Ligands

As P, d or f sets of orbitals have directional character, so these orbitals are no longer
degenerate in presence of an unsymmetrical field.
 The nature of loss of degeneracy depends both on the symmetry of ligands field
and also on the symmetry of the orbitals.
 For transition metals the (n-1)p and (n-1)d orbitals are affected by the ligand field.
As the (n-2) f orbitals are deeply seated I.e. well shielded by the outer electrons so
the effect of electrostatic field of the ligands on f –orbitals are not important.

Splitting of the metal p- and d- orbitals

 In presence of Unsymmetrical ligand field the three fold degeneracy of p-orbitals
and five fold degeneracy of d-orbitals will be lost.
The orbital being repelled by the ligand field will be energetically raised and the
orbitals which are not repelled or less repelled will be energetically lowered.
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Shapes of P & d-orbitals

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Splitting of d-orbitals in Octahedral field

Two types of d-orbitals

 dxy, dyz and dzx orbitals have four lobes concentrated in between axis .So called
as non-axial orbitals and according to group theory known as t2g orbitals(triply
degenerate).
 dx2-y2 and dz2 have four lobes along their respective axes. So called as axial
orbitals and according group theory known as eg orbitals (doubly degenerate)

Six ligands at the six corners of an octahedron and

the metal is at the center.
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 Splitting of d-orbitals in Octahedral field (contd.)

In octahedral complexes, the ligands approach along the axes.

The d-orbitals where electron density is oriented along the axes, dx2-y2 and dz2
are repelled much more by the ligands while the orbitals dxy, dxz, dyz having
electron density oriented in between the axes are repelled lesser by the ligands.
Two sets of orbitals eg (doubly degenerate set) and t2g (doubly and triply
degenerate) are formed due the repulsion between metals and ligands orbitals.
The greater repulsion between electrons in a metal dx2-y2 or dz2 orbital and the
electron pair from ligand, raises the energy of metal orbitals than other three.
The d orbitals split up into t2g and eg where t2g comprises of three orbitals of lower
energy namely dxy, dxz and dyz and eg set having dx2-y2 and dz2 of higher energy.
 The energy separation between the two levels is denoted by ∆o or 10 Dq.
The splitting of orbitals occurs in such a way that the overall energy of the
system remains constant, since the total increase in the energy of eg orbitals
and decrease in energy of the t2g orbitals from the Barry centre is same.

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 Splitting of d-orbitals in Octahedral field (contd.)

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