Академический Документы
Профессиональный Документы
Культура Документы
The VBT does not explain i) the colour and ii) the spectra, of the
complexes. And also it does not explain why the magnetic moment
changes as the temperature changes. The crystal field theory is much more
widely used than the valence bond theory. The model that largely replaced
valence bond theory for interpreting the chemistry of coordination
compounds was the crystal field theory. This theory was first proposed by
Hans Bethe (1929) and modified by J.H. van Vleck (1935). This theory is
also known as ligand field theory.
Pure crystal field theory assumes that the only interaction between the
metal ion and the ligands is an electrostatic or ionic force. The central metal
atom or the ion and the ligands in the complex are considered as point
charges. Then the bonding in a complex may be ion ion attractions (i.e.
between a cation and negative ions). Also the ion dipole attractions may
give rise to bonding. (If the ligand is a neutral molecule such as NH3 and
H2O etc). For example NH3 has a dipole moment. In this molecule N H
bond has the polarities . This theory is successful in interpreting
N H
many important properties of complexes. Symmetry considerations
involved in this theory are identified with those of the molecular orbital
theory.
To understand this theory properly, one should have clear idea of the
geometries of the d orbitals in an atom. There are five d orbitals in the
main energy level. i.e. in any given orbit. These five d orbitals are
conveniently represented as shown in the figures.
The five d orbitals, in an isolated, gaseous metal atom or ion, are
degenerate. If a spherically sym
symmetric
metric field of negative charges (i.e. ligand
ions or the negative end of the dipole) is placed around the metal, the
orbitals remain degenerate still. But all of them will be raised in energy as
compared to these ligands in a field free metal ion, the d orbitals remain
raised in their energies due to the repulsion between the negative field
(from the ligands) and the electrons in th
thee orbitals. The degeneracy of the d
orbitals will be removed. Now the d orbitals are split. The
consequences of this splitting are interpreted by the crystal field theory.
Two types of interactions are possible. overlap of orbitals, overlap of
orbitals; or d p bonding (back bonding) due to overlapping of the
full d orbitals on the metal with the empty p orbital on ligands. In most
transition metals complexes, the coordination is either 6 or 4. Therefore
such complexes are either octahe
octahedral
dral or tetrahedral in shape. The field
produced by the ligands is not spherically symmetrical. Therefore the d
orbitals are not all effected equally by the ligand field.
Under the influence of an octahedral ligand field the d orbitals split into
two groups
roups of different energies.
The extent to which the eg and t2g orbitals are separated in an octahedral
field is denoted by 0 or 10Dq. The average energy of the five d orbitals
is known as Baricentre of the d orbitals and it holds for all complexes,
regardless of geometry.
The d orbitals are split into two groups eg and t2g under the influence of an
applied external field from the ligands. The lobes of the eg orbitals (i.e.
and ) point along the three coordinate axes (, and axes). And the
lobes of the t2g orbitals (
;
and orbitals) point in between the axes.
When six ligands approach the central metal atom or ion along the
coordinate axes i.e. , , , , and directions, the energy of the
and orbitals will increase much more than the increase in the
energy of
,
and orbitals. Thus under the influence of an
octahedral field of ligands, the d orbitals split into two groups. The
difference in energy between the two groups i.e. eg and t2g of orbitals is
given by 0 or 10Dq. This 0 is known as crystal field splitting energy.
Referring the energy of the Bari centre as zero, the eg orbitals are + 0.6 0
above the average level and the t2g orbitals are 0.4 0 below the average.
The magnitude of 0 can be estimated from the UV visible spectrum of
the complex formed. The magnitude of is influenced by three factors.
They are
Ligands are labeled as weak and strong field ligands depending on the
degree of crystal field splitting caused by them. Ligands which cause only a
small degree of splitting are termed w
weak field ligands.
Ex:
And ligands which cause a large degree of splitting are called as strong
field ligands.
Tetrahedral complexes:
t = 0
Square planar
ar complexes:
Now the d orbital splitting be written in the same manner as we did for an
octahedral or a tetrahedral ligand ffield.
Ex: [Ni(CN)4]-2
The ligand field stabilization energy (LFSE) is a measure of the net energy
of occupation of the d orbitals relative to their mean energy.
Example 1:
= 1.20
Example 2:
= 0.6t
Assignment questions:
For both octahedral and tetrahedral complexes practice writing the crystal
field splitting for different dx configurations