Dr.

Sajjad Jahn-Teller [CHEM-305]

Hussain Sumrra Distortion Inorganic Chemistry-II
JAHN-TELLER
DISTORTION
Dr. Sajjad Hussain Sumrra
 Key Points
Background

Introduction

Electronic Configurations

Distortion in Octahedral Complexes

Examples

Distortion in Tetrahedral Complexes

Octahedral Complexes Verses Tetrahedral Complexes

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Background:

• CFT notes that d orbitals have a specific geometry and

orientation in space and claims that d electrons will
residue in the orbitals that are farthest from neighboring
atoms or molecules.

• The presence of d electrons in six- or four coordinate

complexes may cause distortion of the expected
octahedral or tetrahedral configuration.

• The distortion arises because ligands will avoid those

areas around a metal ion in which the d electrons
reside.
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Let us consider the influence of metal d electrons on
structure;
• If there are zero, five (unpaired), or ten d electrons
present in the outer d subshell of an atom, there is no
distortion of the structure of its complexes.
• This is true because empty, half-filled, and filled d
subshells have spherical electrical symmetry; a charged
particle (ligand) on a sphere having the metal at its center
will encounter the same electrostatic force regardless of
its position on the sphere.

• Therefore, the position that a ligand will occupy is not

influenced by d electrons in these cases. 5
Introduction:

• In 1937, Hermann Jahn and Edward Teller postulated

a theorem stating that "stability and degeneracy are not
possible simultaneously unless the molecule is a linear
one," in regards to its electronic state.

• This leads to a break in degeneracy which stabilizes the

molecule and by consequence, reduces its symmetry.

• This is most commonly observed with transition metal

octahedral complexes, however, it can be observed in
tetrahedral complexes as well.
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 THE JAHN-TELLER DISTORTION

The Jahn-Teller Theorem (named after Hermann Arthur

Jahn and Edward Teller), was published in 1937 and
essentially means that:

"Any non-linear molecular system in a degenerate

electronic state will be unstable and will undergo
distortion to form a system of lower symmetry and
lower energy thereby removing the degeneracy"

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 Explanation Jahn-Teller distortion

In the electronically degenerate state, the orbitals are said

to be asymmetrically occupied and get more energy.
Therefore, the system tries to get rid of this extra energy
by lowering the overall symmetry of the molecule i.e.,
undergoing distortion, which is otherwise known as Jahn
Teller distortion.

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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 asymmetrically
occupied.
Example: 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.

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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.

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 where the two axial bonds can be
shorter or longer than those of the equatorial bonds. This
effect can also be observed in tetrahedral compounds. 10
 Electronic Configurations

• For Jahn-Teller effects to occur in transition metals

there must be degeneracy in either the t2g or eg orbitals.
• The electronic states of octahedral complexes are
classified as either low spin or high spin.
• The spin of the system is dictated by the chemical
environment. This includes the characteristics of the
metal center and the types of ligands.

 Low Spin:

There are various electronic configurations for low spin

octahedral complexes.
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The figure illustrates that low spin complexes with d3, d6,
d8, and d10 electrons that do no exhibit Jahn-Teller
distortions as no degeneracy is possible in them.
Examples: Cr3+, Co3+, and Ni2+.
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• Low-spin d6 systems are similar to d3 complexes. The
six electrons completely fill the t2g orbitals.

• Since each of the six ligands is close to two of these

orbitals there is no tendency for distortion and regular
octahedral structures are observed.

• Low-spin d8 complexes are similar to d4 systems. The

last two electrons go into one eg orbital and interact
strongly with ligands that face this orbital.

• Marked distortions occur such that two ligands are much

farther removed from the central metal than are the other
four. In fact, low-spin d8 complexes are almost
invariably square planar. 15
• High Spin:

There are various electronic configurations for high spin

octahedral complexes.

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• The figure illustrates that low spin complexes with d3,
d5, d8, and d10 electrons cannot have Jahn-Teller
distortions.

• In general, degenerate electronic states occupying the

eg orbital set tend to show stronger Jahn-Teller effects.

• This is primarily caused by the occupation of these

high energy orbitals.

• Since the system is more stable with a lower energy

configuration, the degeneracy of the eg set is broken,
the symmetry is reduced, and occupations at lower
energy orbitals occur.
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The distortions that result from the presence of d electrons
in “octahedral” complexes are summarized in Table.

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 Distortion in Octahedral Complexes

The degeneracy of orbitals can be removed by lowering the

symmetry of molecule. This can be achieved by elongation
of bonds along the z-axis (Z-out distortion) or by
shortening the bonds along the z-axis (Z-in distortion).
Thus, an octahedral symmetrical molecule is distorted to
tetragonal geometry.

The octahedral complex

will either elongate or
compress the z ligand
bonds as shown

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 Elongation (Z-out 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.
• Elongation Jahn-Teller distortions occur when the
degeneracy is broken by the stabilization (lowering in
energy) of the d orbitals with a z-component, while the
orbitals without a z-component are destabilized (higher
in energy) as shown.

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Elongation and Compression of Octahedral Complexes

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• Notice that the two axial bonds are both elongated and
the four shorter equatorial bonds are the same length as
each other.

Example:
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 occurs when the degeneracy occurs in eg level.
• However, it is observed that z-out distortion is more
preferred.

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 Compression (Z-in 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.

• Compression Jahn-Teller distortions occur when the

degeneracy is broken by the stabilization (lowering in
energy) of the d orbitals without a z-component, while the
orbitals with a z-component are destabilized (higher in
energy).
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This is due to the z-component d orbitals having greater
overlap with the ligand orbitals, resulting in the orbitals
being higher in energy. Since the dz2 orbital is antibonding,
it is expected to increase in energy due to compression.
The dxz and dyz orbitals are still nonbonding, but are
destabilized due to the interactions.

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 Examples of Distortion in Octahedral Complexes

• The complex [Ti(H2O)6]3+

contains one d electron; this
electron will repel ligands that
are near it.

• If this complex has the expected octahedral geometry,

the one electron should be in a t2g orbital, one which
points between H2O ligands.
• If the electron were in the dxy orbital, one would expect
the ligands in the xy plane to be repelled.
• This would lead to four long Ti—H2O bonds (and two
short ones along the z axis).
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• Four long bonds and two short ones would also be
expected if the electron were placed in a dxz or dyz
orbital.

• Since the t2g orbitals point between ligands, one might

expect that the effect of the presence of electrons in
these orbitals would be small.

• In fact, unequal bond lengths in complexes such as

[Ti(H2O)6]3+ have not been detected by X-ray
diffraction studies.

• However, the visible spectra of these complexes do

provide evidence of a slight distortion
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 Examples of Distortion in Octahedral Complexes

In octahedral d3
complexes, such as
[Cr(H2O)6]3+, each t2g
orbital contains one electron.

• Each of the six ligands in an octahedral array would be

near two of these d electrons, and hence all would
experience the same repulsion.
• No distortion is expected or observed.

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 Examples of Distortion in Octahedral Complexes

In [Cr(H2O)6]2+, which is a d4
high-spin system, the first three
electrons go in t2g orbitals and
produce no distortion of an
octahedral structure.
• The fourth electron goes in an eg orbital that points
directly at ligands.
• If the electron resides in a dz2 orbital, the ligands on the
z axis are repelled; if it resides in the dx2–y2 orbital, the
four ligands in the xy plane are repelled.
• In fact, six coordinated d4 metal complexes have
distorted structures in all cases studied.
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Examples of Distortion in Octahedral Complexes

For example, in MnF6

each manganese(III) is
surrounded by six F– ions
so arranged that four are
closer to the Mn3+ ion than
are the other two.

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• It should be clear that high-spin d6, d7, d8, and d9
systems are similar to d1, d2, d3, and d4 systems,
respectively.
• Six-coordinated complexes of d9 metal ions exhibit
distortions similar to those of d4 complexes.
• The most common examples are copper(II)
complexes.

In [Cu(NH3)4]2+, the
tetragonal distortion is so
marked that the square
planar tetraammine
complex results.

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• Note, however, that solvent molecules occupy
positions above and below the plane in solutions of
complexes of this type; these solvent molecules are
farther from the metal ion than are groups in the
square plane.

• The distortion of symmetrical structures resulting

from partially filled electronic energy levels (in this
case the d sublevel) are called Jahn–Teller
distortions.

• The distortions of octahedral structure observed in

important low-spin configurations should also be
considered.
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 Distortion in Tetrahedral Complexes

• Tetrahedral structures are also observed in metal

complexes; however, they are less common than
octahedral and distorted octahedral configurations.

• Two exceptions must be noted. As we have seen, four

coordinated low-spin d8 complexes are square planar,
as are many four coordinated d9 and high-spin d4
complexes.

• Tetrahedral d3, d4, d8, and d9 systems should exhibit

marked Jahn–Teller distortions; however, very few
examples of this type of compound exist.
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• The tetrahedral crystal field splitting (Δt) is
apparently too small to cause spin pairing.

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Octahedral Complexes Verses Tetrahedral Complexes
• The tendency for large coordination numbers is opposed
by steric and electrostatic (or Pauli) repulsion between
ligands. However, that the first-row transition
elements are frequently six-coordinated.

• Four-coordination is observed primarily in complexes

containing several large anions, such as Cl–, Br–, I– and
O2–, or bulky neutral molecules.

• The most common and important complex ions are

hydrated metal ions. Isotope dilution techniques were
used to show that Cr3+ and Al3+ are bonded rather
firmly to six water molecules in aqueous solutions. 34
• The interpretation of the visible spectra of solutions of
transition metal ions using CFT indicates that ions such
as V2+, Mn2+, Fe2+, Co2+, Ni2+, V2+, Cr2+, and Fe2+ are
octahedral [M(H2O)6]m+ species.

• For non-transition metal ions it has been more difficult

to obtain structural information. However, nuclear
magnetic resonance spectroscopy demonstrates that
Be2+ in aqueous solution is surrounded by four water
molecules.

• These data support the importance of six coordination.

The only exception cited here is Be2+, an element which
obeys the octet rule.
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