First Row Transition
Metals
What are the advantages of valence bond theory, and why
was there a need for another theory?
• Valence bond theory explains chemical bonding using electron
pairing and orbital hybridization.
• Orbital hybridization is the concept of mixing atomic orbitals into
new hybrid orbitals of different energies and shapes. These hybrid
orbitals are suitable for pairing of electrons to form chemical
bonds.
• Orbital hybridizations and valence shell electron-pair repulsion
theory (VSEPR) are very useful in the explanation of molecular
structure and atomic bonding properties.
• However, the valence bond theory does not provide an
explanation for the spectral bands of metal complexes.
• The valence bond approach fails to explain the magnetic moment
of most complexes.
Shapes of d-orbitals
The five d-orbitals are not
identical and their shapes may
be divided into two sets:
The three t2g orbitals have
identical shape and point
between the x, y and z axis
The two eg orbitals have
different shapes and point
along the axis
The five d-orbitals of an isolated, gaseous metal ion are dege-
nerate. If a spherically symmetric field of negative charges is
placed around the metal, the orbitals will remain degenerate,
but all of them will be raised in energy as a result of repulsion
between the negative field and the negative electrons in the
orbitals.
If the field results from the influence of real ligands, the sym-
metry of the field will be less than spherical and the degenera-
cy of the orbitals will be removed and the d-orbitals are no
longer degenerate.
It is the splitting of d-orbital energies and its consequence
that are at the heart of crystal field theory.
Crystal-field theory is a primitive theory,
and strictly speaking it applies only to
ions in crystals; however, it can be used
to capture the essence of the electronic
structure of complexes in a
straightforward manner.
Crystal Field Theory
The crystal field theory is the most widely accepted theory to explain
metal to ligand bonding in complexes.
It assumes that the attraction between the central metal ion and the
ligands in a complex is purely electrostatic.
The ligands may be negative in charge or may be neutral molecules
which have lone pair of electrons.
The electrons of the central metal ions are under repulsive forces
from those on the ligand.
The electrons occupy the d-orbitals furthest away from the direction
of approach the ligands.
Key features of CFT
In crystal field theory, the coordination bond is regarded
as a purely ionic model, wherein the anions and cations
are rigid, non-polarizable spheres of integral charge (point
charges).
In such model, the electrons of the central metal ion are
subject to a potential from the coordinated ligand atoms.
Each negative charge of the surrounding ligands induces
an electrostatic potential on the electrons of the central
ion, that potential can be calculated.
The potential formed nearby an ion is a characteristic
feature of a lattice, and such a lattice could happen only in
a crystal, and in coordination cluster.
Octahedral Complexes
Complete set of d-orbitals in an octahedral field produced by six ligands. The eg
orbitals are shaded and the t2g orbitals are unshaded. dz2 orbital omitted.
CY 5011 Jul-Nov 2022 DC
In an octahedral complex, the metal is at the center of the
octahedron and the ligands are at the six corners.
The lobes of the eg orbitals point along the x, y and z axis
and the lobes of the t2g orbitals point in between the axis.
Approach of the six ligands along the Cartesian axis will
increase the energy of the eg orbitals much more than
energy of the t2g orbitals since the eg orbitals point along
the axis
Under the influence of an octahedral field
the d-orbitals split into two groups of
different energies
Crystal field splitting of energy levels in an octahedral field
The weighted mean of these two sets of
perturbed orbitals is taken as the zero and
is called the Bari centre.
The difference in energy between the two
d-levels is given either of the symbols: Δ0
or 10 Dq
The eg orbitals are +0.6Δ0 above the Bari
centre and the t2g orbitals are -0.4Δ0 below
the Bari center
Diagram of the energy levels of d-orbitals in an octahedral field
For an electron in the dz2 orbital of the metal ion, the energy can be expressed in terms of a
quantum mechanical integral following the same procedure for calculating the average or
expectation value for a dynamical variable. In this case, the calculation involves the wave
function for the orbital and the operator for potential energy, V
R = distance of ligands and metal
a4 = expectation value of finding
an electron in dz2 orbital at R
Dq derives for quantum mechanic description of the electrostatic
model of crystalline fields and is connected to the radial electron
density of the d-electrons, the charge of the metal and the distance
of ligands and metal. The term Dq is the product of two terms D and
q and is called Differential of quanta implying the energy. The word
D has been coined from D State (L=2 ).