Co-ordination compound III

Jahn –Teller Effect

• The Jahn-Teller effect is a geometric distortion of a non-linear molecular system that

reduces its symmetry and energy.

• This distortion is typically observed among octahedral complexes

• This effect is observed when two axial bonds can be shorter or longer than those of the
equatorial bonds.

• This effect is dependent on the electronic state of the system

 JAHN TELLER THEOREM

• In 1937, Hermann Jahn and Edward Teller postulated a theorem.

• Stability and degeneracy are not possible simultaneously unless the molecule is a linear one.

• Any non-linear molecule in an orbitally degenerate electronic state which is asymmetrically

occupied would be unstable and it would get stabilized by undergoing distortion in its
geometry and thus by causing a split in its orbitally degenerate electronic state.

• The lowering of symmetry always occurs in a manner that results in decrease in the energy of
the system.
Asymmetrically occupied electronically degenerate orbitals
• An electronically degenerate state represents the availability of more than one degenerate orbital for an
electron. In this condition the degenerate orbitals are said to be asymmetrically occupied.
In octahedral symmetry, the d1 configuration is said to be electronically degenerate since three t2g orbitals
with same energy are available for the electron to occupy. In this condition, the degenerate orbitals are also
said to be asymmetrically occupied by electrons.

Whereas the d3 configuration in octahedral geometry is non-degenerate and symmetric. It is not possible to put two
electrons in one orbital, which is against of Hund's rule of maximum multiplicity.
Statements of Jahn-Teller distortion

• If the ground electronic state of a non-linear molecule is electronically

degenerate, the complex will distort itself to remove the degeneracy and
achieve lower energy.
• Any non-linear molecule in an electronically degenerate state will be
unstable and will undergo distortion to regain stability by decreasing the
symmetry and decreasing energy.
• If the ground electronic state of an orbitally degenerate state is
asymmetrically filled, then the complex distorts itself to remove the
degeneracy and achieve lower energy.
Jahn – Teller Distortion
In the electronically degenerate state, when the orbitals the orbitals are said
to be asymmetrically occupied and hence get more energy. Therefore, the
system tries to get rid of extra energy by lowering the overall symmetry of the
molecule i.e., undergoing distortion, which is otherwise known as Jahn Teller
distortion (effect).
Degenerate electronic state with asymmetric distribution of electrons.
Less stability and more energy.
Molecule tries to attain stability by decreasing energy
Decreasing energy is done by removing the degeneracy.
Molecule undergoes distortion to remove degeneracy
 JAHN –TELLER DISTORTION

Cu2+ complexes Eg: [CuF6]4-, [Cu(H2O)6]2+

d9 electronic state 6t2g 3Eg

• The last electron may occupy either dz2 or dx2-y2 orbitals of eg set.
• If it occupies dz2 orbital, most of the electron density will be concentrated between the metal and the two ligands on the
z axis.
• Thus, there will be greater electrostatic repulsion associated with these ligands than with the other four on xy plane.
• This asymmetric distribution of the electron density may increase the overall energy of the system.
• System will try to decrease the energy by removing the degeneracy of the molecule.
• The degeneracy of orbitals can be removed by lowering the symmetry of molecule.
• This can be achieved by either elongation of bonds along the z-axis (Z-out distortion) or by shortening the bonds along
the z-axis (Z-in distortion).
• Thus an octahedrally symmetrical molecule is distorted to tetragonal geometry.
• To get rid of this, the complex suffers elongation of bonds on z-axis and thus lowers the symmetry.
• Conversely, occupation of the dx2-y2 orbital would lead to elongation of bonds along the x and y axes.
 JAHN –TELLER DISTORTION

Cu2+ complexes Eg: [Cu(H2O)6]2+

d9 electronic state 6t2g 3Eg

 JAHN –TELLER DISTORTION

Tetragonal distortion - z out distortion – Energy level diagram

Because of the elongation in the z direction

repulsion experienced by electrons in dz2
orbitals by ligand electrons is less compared to
the repulsion experienced by electrons in the
dx2-y2 orbital.
Due to this dz2 orbital will have less energy
compared to dx2-y2
This way degeneracy of eg orbitals is lifted.
 JAHN –TELLER DISTORTION

Tetragonal distortion - z in distortion – Energy level diagram

• Because of the compression along

the z direction repulsion
experienced by electrons in dz
orbitals by ligand electrons is more
compared to the repulsion
experienced by electrons in the
dx2-y2 orbital.
• Due to this dz2 orbital will have
more energy compared to dx2-y2
• This way degeneracy of orbital is
lifted.
 JAHN –TELLER DISTORTION

Tetragonal elongation
Elongated z orbitals
Z-out distortion
 JAHN –TELLER DISTORTION

hexaaquacopper(II) complex ion, [Cu(H2O)6]2+, which

might otherwise possess regular octahedral geometry.
The two axial Cu−O distances are 238 pm, whereas the
four equatorial Cu−O distances are ~195 pm.
This geometry is common in crystal structures; the
geometry in solution is uncertain
 Condition for JAHN-TELLER distortion
Asymmetric distribution electrons in a degenerate orbital
Asymmetric electron distribution in Eg orbital causes strong JAHN-TELLER
distortion.
As the ligand approaches the axis more repulsion is experienced by orbitals along
the axis

Red -symmetric distribution

Black-Asymmetric distribution
JAHN –TELLER DISTORTION
JAHN –TELLER DISTORTION

Single peak corresponding to t2g – eg transition

in complex without distortion.
Two peaks or a hump and a peak will appear in
distorted octahedra
 Effect of Jahn –Teller distortion on electronic spectra of the complexes
Ti3+ - 3d1

dz2
eg

dx2-y2

Degerate d orbitals

dxz, dyz

t2g dxy

One peak and one shoulder present in the spectrum. For octahedral symmetry there is one electronic transition
in the visible region. After jahn –teller distortion there are two electronic transitions in the visible region and one
in the infrared
Crystal field splitting in square planar complexes
Crystal field splitting in square
planar complexes

Ni2 +

Square Planar complexes always form low spin

complexes
Δ0 is the difference between dx2-y2 and dxy
orbitals
Δ0 > P

Square planar geometry is observed in d8

complexes(Ni2+ and Pt2+ compounds)
•
 Experimental evidence for metal – ligand covalent bonding

1. Electron spin resonance (ESR)spectra

2. Nuclear magnetic resonance (NMR) spectra

3. Interelectronic repulsion (Nephelauxetic effect)

4. Linde’s splitting factor g

5. Nuclear quadrupole resonance studies (NQR)

6. Intensity of d-d transitions.

 Evidence for metal – ligand covalent bonding
1. Electron spin resonance (ESR)spectra : ESR spectroscopy is a branch of electron spectroscopy in which molecules
having electrons with unpaired spin absorbs radiations of microwave frequency

ms = + ½

S= ±½ Microwave energy

In the absence of
magnetic field ms = - ½
In presence of

Absorption
magnetic field

Magnetic field
Ir electronic configuration = [Xe] 5d7 6s2
Ir4+ electronic configuration = [Xe] 5d5

t2 e
g g

Magnetic field
The nephelauxetic effect refers to the
phenomenon in transition metal complexes
where the binding of ligands to a metal ion
results in an expansion of the d-orbitals of
the metal. This expansion is attributed to the
electron-electron repulsion between the
electrons in the metal's d-orbitals and the
electrons donated by the ligands.
The Racah parameters (B) are a set of parameters used in atomic and molecular spectroscopy to describe the
amount of total electrostatic repulsion in an atom that has multiple electrons.

It is observed Racah parameters for complexes are less for complexes compared to free ions.
This indicates the delocalization of ligand electrons via covalent bonding.
 Experimental evidence for metal – ligand covalent bonding
Nuclear magnetic (NMR)spectra

ms = + ½

S= ±½ Radiofrequency

In the absence of
magnetic field ms = - ½
In presence of

Absorbance
magnetic field

Magnetic field
 Experimental evidence for metal – ligand covalent bonding
Nuclear magnetic (NMR)spectra

In NMR spectrum shift of spectra occurs due to the spin of electron surrounding it.

If there is no covalent bonding or delocalization, shift of NMR spectrum of ligands are only due to spin of
ligands and shift of signals in metal spectrum by spin of electrons on the metal atom.

NMR signals of some ligands in metal complexes are remarkably affected by the unpaired electrons
present in the central metal atom.

NMR studies of flouro complexes of paramagnetic clearly indicate that the spin of unpaired electrons of
the metal ion interact with the nuclear spin of 19F . The interaction of electron spin and nuclear spin is
possible only if unpaired electron spends more time on 19F nucleus. This is possible through the
overlapping orbitals of ligand and metal ion through covalent bonding.
Ligand Field Theory

Crystal field theory

Could not explain covalent nature of the M-L bond.
Only d electrons are involved in bonding.
Orbitals of ligands are not taken into consideration.
π bonding in molecules can not be explained

A third model, based on molecular orbital theory, was therefore developed which is known
as ligand-field theory.
The ligand-field theory is more powerful than either the valence-bond or crystal-field theories.
Unfortunately, it is also more abstract.
Ligand field Theory
Summary

• Ligand field theory was postulated by Orgel and Griffith in 1950.

• It is a modified version of crystal field theory and molecular orbital theory.

• The two major aspect of ligand field theory is σ bonding and π bonding.

• CFT works well with small ligand like F-, Cl- and H2O but not with neutral ligands like
carbonyl (CO).

• Ligand field theory explains well the π bonding nature of CO and CN ligands
Ligand Field Theory
Molecular orbital theory – Recap

• Atomic orbital combine to form molecular orbitals.

• If “n” no of atomic orbitals overlap with each other, then “n” no of molecular orbitals are formed in which
half are bonding molecular orbital (BMO) and half are antibonding molecular orbitals (AMO).

• Atomic orbitals overlap to form molecular orbitals only if the participating atomic orbitals must
1. Have similar energy
2. Have similar symmetry
3. Overlap appreciably

• In case of polyatomic molecules, peripheral atoms will first combine with each other forming group orbitals.

• Ligand group orbital overlap with atomic orbitals of central atom.

Ligand field Theory
Postulates
Ligand field Theory
When the MOs are made up of 2 component orbitals of different energies

antibondi
ng

Metal
orbitals
Ligand
orbitals

Bondi
ng

Rule of thumb
The bonding orbital looks more like the lower energy component
The antibonding orbital looks more like the higher energy component
 Consider for an Octahedral complex(Oh): In an octahedral complex there are six sigma (σ) bonds. The
formation of this six (σ) bonds takes place as:
1. The central metal atom of transition elements contains 9 valence atomic orbitals say one ns, three np
and five (n-1)d. They are ns, npx, npy, npz, (n-1)dxy, (n-1)dyz, (n-1)dzx, (n-1)dx2-y2 and (n-1) dz2 Out of
these 9 orbitals, only 6 orbitals should overlap with the ligand orbitals to form six σ bonds (because
there are only six ligands in an octahedral complex).

2. According to the symmetry, the nine atomic orbitals of metal atom in an Oh complex can be
transformed as
S orbital as → a1g
px, py, pz as → t1u
dxy, dyz, dzx as →t2g
dx2-y2, dz2 → eg

3. As ligands are approaching along the axes in an octahedral complex, the six atomic orbitals i.e, a1g, t1u,
and eg can form σ bond as their lobes are along the axes whereas the three atomic orbitals say t2g remains
as non bonding since their lobes are between the axes. However they can form П (pi) bond by sideways
overlapping if there exist possibility of П bonding.
4) The orbitals of ligands are combined to overlap with the metal orbitals to form σ bonds, they are
collectively called ligand group orbitals (LGO) and hence they should have the same symmetry as a1g, t1u,
and eg.

5) As ligands orbital contained electrons and donated to the central atom in the formation of σ bonds their
atomic orbitals are lower in energy than the metal atomic orbitals.

6) As the overlap of 4s and 4p metal orbitals with the ligand orbitals is considerably better than that of 3d
(eg) orbital, the bonding a1g, and t1u molecular orbitals are lowest in energy and the antibonding a1g * ,
and t1u * are highest in energy
 Octahedral -ML6

T2g can form only π bonds as their lobes are

oriented in between axis

np

ns

(n-1)d

Σa1g Σ t1u Σ eg

6 ligand orbitals

Metal ion Ligand

ML
Splitting energy Δ0 is the energy differenced
between t2g non bonding and antibonding eg*
As in the case of CFT splitting Δ0 depends on
• size of metal ion
• charge of metal ion
• the nature of ligand

Depending on Δ0 value high spin and low spin

complexes are formed.
Colour of complex is due to the excitation of
electrons in nonbonding orbitals to antibonding
eg*Orbital.
Here colour is not due to forbidden d-d
transitions but transition between nonbonding
and antibonding orbitals.
 Tetrahedral ML4 complex

Ligand approach through in between axis

Metal orbital which lie in between axis will overlap with ligand orbitals.
Tetrahedral ML4 complex
Ligand field Theory
Octahedral -ML6

S, P and d orbital of metal ion z -axis

participate in bonding
y -axis
S orbital- a1g
P orbital – t1u
d orbital X -axis X -axis
dx2-y2 eg
dz2 - t2g
y -axis

z -axis
a – singly degenerate
e - doubly degenerate
Ligands approach along the axis
t - triply degenerate

u- ungerade symmetry element absent

g is gerade – symmetry present
Ligand field Theory Octahedral -ML6

Since the ligand is approaching along the axis metal orbitals which are along the axis will form bonding and antibonding
molecular orbital with ligand orbitals.

Oriented along the axis

Interact with ligand orbital
forming bonding and
antibonding orbitals

a1g T1u eg

Oriented in between axis

No interaction with ligand orbital
Non bonding
Ligand field Theory
Application of Ligand filed theory to octahedral complexes
σ bonding
Spectroscopic term symbols for different orbitals

Σa1g
a1g
Ligand field Theory
Application of Ligand filed theory to octahedral complexes
σ bonding
Spectroscopic term symbols for different orbitals

t1g Σ t1u
Ligand field Theory
Application of Ligand filed theory to octahedral complexes
σ bonding
Spectroscopic term symbols for different orbitals

eg Σ eg
Ligand field Theory
Application of Ligand filed theory to octahedral complexes
σ bonding
Spectroscopic term symbols for different orbitals

Ligand approach along axis

t2g T2g orbitals are not aligned along the axis
So they do not participate in σ bonding