4th Sem CHE-HC-4016:
Jahn Teller Distortion
Prepared by
Dr.Manash Jyoti Deka
What is electronically degenerate state?
An electronically degenerate state represents the availability of more than one degenerate
orbitals for an electron. In this condition the degenerate orbitals are said to be asymmetrically
occupied.
E.g. 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.
In the electronically degenerate state, 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).
E.g. In case of octahedral d9 configuration, 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.
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.
* The Jahn Teller effect is mostly observed in octahedral environments. Theoretically, the
electronic degeneracy in octahedral symmetry is possible in all the configurations except d3,
d8, d10, high spin d5 , and low spin d6 configurations.
However, considerable distortions are usually observed in high spin d4, low spin d7 , and
9
d configurations in the octahedral environment. It is because the Jahn Teller distortion is
usually significant for asymmetrically occupied eg orbitals since they are directed towards the
ligands and the energy gain is considerably more.
* In case of unevenly occupied t2g orbitals, the Jahn Teller distortion is very weak since
the t2g set does not point directly at the ligands and therefore the energy gain is much less.
E.g. d1; d2; low spin d4 & d5; high spin d7 & d7 configurations.
Because of same reason, the tetrahedral complexes also do not exhibit Jahn-Teller
distortion. Again, in this case also the ligands are not pointing towards the orbitals directly
and hence there is less stabilization to be gained upon distortion.
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.
Z-out Jahn-Teller distortion: In this case, the energies of d-orbitals with z factor ( i.e.,
dz2, dxz, dyz ) are lowered since the bonds along the z-axis are elongated. This is the most
preferred distortion and occurs in most of the cases, especially when the degeneracy occurs in
eg level.
E.g. Usually the octahedral d2, d4 high spin, d7 low spin, d8 low spin & d9 configurations
show the z-out distortion.
Theoretically it is not possible to predict the type of distortion that occurs when the
degeneracy occurs in eg level. However it is observed that z-out distortion is more preferred.
Z-in Jahn-Teller distortion: In this case the energies of orbitals with z factor
are increased since the bonds along the z-axis are shortened. This type of distortion is
observed in case of octahedral d1 configuration. The only electron will now occupy the
dxy orbital with lower energy.
E.g. The octahedral d1 configurations like Ti(III) in [Ti(H2O)6]3+ can show z-in distortion
(theoretically?). In this case, the z-out distortion do not remove the degeneracy since even
after distortion there are still two degenerate orbitals i.e., dxz and dyz available for the electron
to occupy. See the following diagram.
Also remember that the Jahn-Teller theorem does NOT predict how large a distortion
should occur.
Static Jahn-Teller distortion: Some molecules show tetragonal shape under all
conditions i.e., in solid state and in solution state; at lower and relatively higher temperatures.
This is referred to as static Jahn-Teller distortion. It is observed when the degeneracy occurs
in eg orbitals. Hence the distortion is strong and permanent.
Dynamic Jahn-Teller distortion: In some molecules, the distortion is not seen either due
to random movements of bonds which does not allow the measurement within a time frame
or else the distortion is so weak as to be negligible. However, the distortion can be seen by
freezing the molecule at lower temperatures. This condition is referred to as dynamic Jahn-
Teller distortion.
E.g.
1) The complexes of the type M2PbCu(NO2)6 show dynamic Jahn-Teller distortion.
Here, M= K, Rb, Cs, Tl;
They show tetragonal symmetry at lower temperatures due to static Jahn-Teller distortion.
But at higher temperatures, these molecules appear octahedral due to the dynamic Jahn-Teller
effect.
2) The complex [Fe(H2O)6]2+ shows dynamic Jahn-Teller distortion and appears
octahedral. In this case, the distortion is small since the degeneracy occurs in t 2g orbitals.
Remember Fe2+ in above complex is a high spin d6 system with t2g4 eg2 configuration.
1) Jahn-Teller distortion in complexes formed by Cu(II) ions:
a) Tetragonal structure of Cu(II) complexes: The Cu(II) ion is a d9 system and
expected to show Jahn-Teller distortion and depart considerably from octahedral geometry.
The Cu(II) ion in the aqueous medium is surrounded by six water molecules in tetragonal
geometry i.e., four of which are at the corners of square plane and are at shorter distances
with stronger interactions, whereas, the remaining two are weakly interacting with the metal
ion at distant axial positions.
b) Structure of hydrated copper(II) sulphate, CuSO4.5H2O and other Cu(II)
complexes: In the solid CuSO4.5H2O, the copper ion is surrounded by four water molecules
in square planar geometry. There are also weak interactions with the sulphate ions in the axial
positions. The 5th water molecule is hydrogen bonded to the sulphate ion. That means the
two water molecules on the axial positions are completely eliminated and substituted by
sulphate ions while forming the solid.
Note: Due to interactions with these ligands, the d orbitals are split into different energy
levels, which makes d-d transitions possible. It absorbs red color and transmits blue color
during the d-d transition. But upon heating, all the water molecules are lost, which makes all
the d orbitals degenerate again. Hence the anhydrous CuSO4 is colorless.
c) Extra stability of Cu2+ ions: The relative stabilities of complexes formed by high spin
divalent first row transition metal ions is given by Irving-Williams series. The stability order
is shown below:
Mn(II) < Fe(II) < Co(II) < Ni(II) < Cu(II) > Zn(II)
The extra stability of Cu(II) ion can be explained by taking into account of Jahn-Teller
distortion of this d9 ion.
d) Other examples: Because of Jahn-Teller distortion:
* In the crystalline KCuF3, the two Cu- F distances are at 1.96 A0 and the remaining four
Cu - F distances are at 2.07 A0. It is a case of Z-compression.
* In [Cu(hfacac)2(bipy)], there are two short Cu-O bonds and two long Cu–O
bonds. (where hfacac = hexafluoroacetylacetone anion; bipy = 2,2’-bipyridine). It is an
example for Z-out distortion.
* Cu(II) cannot form [Cu(en)3]2+ since JT distortion brings strain into the ethylene
diamine molecule that is added along z-axis. Hence only [Cu(en)2(H2O)2]2+ is formed.
2) The splitting of absorption bands in the UV-VIS spectra of complexes due to Jahn-
Teller distortion:
E.g. The absorption band in the electronic spectrum of aqueous Ti(III), a d1 octahedral
system, is not symmetric but rather shows a distinct broad shoulder. It is because of Jahn-
Teller distortion.
The Jahn-Teller distortion is negligible in case of degenerate t2g orbitals in the ground
state. Hence no distortion in the ground state. But when the electron gets excited, the
configuration now becomes t2g0 eg1, which is again degenerate. Hence in the excited state, the
Jahn Teller distortion is possible. Now the promotion of electron may occur to either of the
two non degenerate eg orbitals, the dz2 and dx2-y2. Thus, two transitions are possible. But a
shoulder appears since the energy difference between two transitions is small.
3) Coordinatively labile nature of [Cr(H2O)6]2+ & [Co(NH3)6]2+:
The [Cr(H2O)6]2+ undergoes substitution easily since the Cr(II) ion is a high spin
4
d system with one electron in the eg orbital. Hence it is electronically degenerate and shows
Jahn-Teller distortion. Hence the hydrated Cr(II) ion is coordinatively labile.
On the same lines, the easy substitution of [Co(NH3)6]2+ by water molecules can be
explained. In this case the Co(II) ion is coordinatively labile since it is a low spin octahedral
d7 ion which is degenerate in eg set. Hence it undergoes J-T distortion and is labile.
4) Disproportionation of Au(II) salts:
Au(II) ion is less stable and undergoes disproportionation to Au(I) and Au(III) even
though the Cu(II) and Ag(II) ions are comparatively more stable. One may expect same
stability since all are d9 systems and undergo the Jahn-Teller distortion.
However, the Δ value increase down the group. Hence, in Au(II) ion, it reaches a
maximum, which causes high destabilization of the last electron, which is now occupying the
dx2-y2. This makes Au(II) reactive, which may undergo either oxidation to Au(III), a
d8 system or reduction to Au(I), a d10 system.
The d8 system, Au(III) is stable as the electron from the dx2-y2 is removed. Mostly it
prefers square planar geometry and more stable than both Au(II) and Au(I). The d10 system,
Au(I) favors mostly linear geometry with coordination number = 2.
Question-Why do the d9 systems usually not undergo complete distortion to square planar
geometry?
Answer: Usually, the d9 systems are tetragonal with elongated bonds on z-axis and do not
undergo complete distortion to square planar. It is because the last electron will be placed in
highly destabilized dx2-y2 if they get square planar geometry. But the low spin d8 complexes
may undergo complete distortion to square planar geometry.
Question-1: Which metal complex ion is expected to be subject to a Jahn-teller
distortion?
A) Cu2+
B) Ni2+
C) Ca2+
D) Cr3+
Answer: A
Question-2: Which of the following does not show octahedral geometry,
1) [Cu(CN)4]2+
2) XeF4
3) [NiCl4]2-
4) All
Answer: 4
Question-3: Strong Jahn-teller distortion is not observed for octahedral complexes of:
1) Cu2+
2) Low spin Cr2+
3) High spin Mn3+
4) High spin Cr2+
Answer: 2
Question-4: Which of the following shows strong Jahn teller distortion?
1) Fe3+
2) High spin Co2+
3) Ti2+
4) Low spin Co2+
Answer: 4
Question-5: Jahn teller effect is not observed in high spin complexes of:
A) Mn2+
B) Cr2+
C) Cu2+
D) Fe3+
Answer: A
Question-6: Which metal complex ion is expected to be subject to a Jahn teller
distortion?
1) Low spin Co2+
2) High spin Cr2+
3) Ti2+
4) All
Answer: 4
Question-7: Which of the following d-configuration shows strong distortion from
octahedral geometry?
1) d1
2) d2
3) d9
4) None
Answer: 3
Question-8: Why does the absorption spectrum of aqueous [Ti(OH2)6]3+ exhibit a broad
band with a shoulder?
1) Due to Jahn-Teller distortion in the ground state
2) Due to Compton effect
3) Due to jahn-Teller distortion in the excited state
4) Due to square planar geometry
Answer: 3
