5.

11|TETRAGONAL DISTORTION OF OCTAHEDRAL COMPLEXES

(JAHN-TELLER DISTORTION)
The shape of transition metal complexes is determined by the tendency of electron pairs to occupy posi
tions as far away from each other as possible. This is the same as for the main group compounds and
complexes. In addition, the shapes of transition metal complexes are affected by whether the d orbitals are
symmetrically or asymmetrically filled.
Repulsion by six ligands in an octahedral complex splits the d orbitals on the central metal into t,, and e
levels. It follows that there is a corresponding repulsion between the d electrons and the ligands. If the d
electrons are symmetrically arranged, they will repel all six igands equally. Thus the structure will be a
completely regular octahedron. The symmetrical arrangements of d electrons are shown in Table 5.13.
 Table 5.13 Symmetricalelectronic arrangements
Electronic configuration e Nature of ligand field Examples

Strong or weak
Ti'O,.[TE,J
[T'CI,
[C-"(oxalate),}
EEEB Strong or weak
[C-"(H,0).P"
[Ma"FJ
Weak
[Fe"F,
[Fe"(CN),J
Strong
[Co"(NH,).J

d Weak
[Ni"E,]
[Ni"(H,0),
Strong or weak
[Zn"(NH,).P*
[Zn"(H,0),.J
Allother arrangements have an asymmetrical arrangement of d electrons. If the d electrons are asym
metrically arranged, they will repel some ligands in the complex more than others. Thus the structure is dis
torted because some ligands are prevented from approaching the metal as closely as others. Thee, orbitals
point directly at the ligands. Thus asymmetric filling of the e, orbitals results in some ligands being repelled
more than others. This causes a significant distortion of the octahedral shape. In contrast the t,, orbitals do
not point directly at the ligands, but point abetween the ligand directions. Thus asymmetric filling of the t,.
orbitals has only a very small effect on the stereochemistry. Distortion caused by asymmetricfilling of the
I,, orbitals is usually too small to measure. The electronic arrangements which will produce a large distortion
are shown in Table 5.14.

Table 5.14 Asymmetrical electronic arrangements

Electronic configuration 29 Nature of ligand field Examples
Weak field (high-spin complex) Cr (+ II), Mn (+ III)

Strong field (low-spin complex) Co (+ II), Ni(+ II)

Either strong or weak Cu (+ II)

The two e, orbitals d, and d, are normally degenerate. However, if they are asymmetrically filled
then this degeneracy is destroyed, and the two orbitals are no longer equal in energy. If the d, orbital con
tains one more electron than the dorbital then the ligands approaching along +z and-z will encounter
greater repulsion than the other four ligands. The repulsion and distortion result in elongation of the octa
hedron along the z axis. This is called tetragonal distortion. Strictly it should be called tetragonal elonga
tion. This form of distortion is commonly observed.
If the d,: ; orbital contains the extra electron, then elongation will occur along the x and y axes. This
means that thé ligands approach more closely along the z axis. Thus there will be four long bonds and two
short bonds. This is equivalent to compressing the octahedron along the z axis and is called tetragonal com
pression. Tetragonal elongation is much more common than tetragonal compression, and it is not possible
to predict which will occur.
For example, the crystal structure of CrF, is a distorted rutile (TiO,) structure. Cr* is octahedrally sur
rounded by six F,and there are four Cr-Fbonds of length 1.98-2.01 , and two longer bonds of length
2.43 . The octahedron is said to be tetragonally distorted. The electronic arrangement in Cr is d. F is
a weak field ligand, and so the t, level contains three electrons and the e, level contains one electron. The
d orbital has four lobes whilst the d, orbital has only two lobes pointing at the ligands. To minimize
repúlsion with the ligands, the single e, electron will occupy the d, orbital. This is equivalent to splitting
the degeneracy of the e, level so that d, is of lower energy, i.e. more stable, and d ,is of higher energy, i.e.
less stable. Thusthe two ligands approaching along the +z and-z directions are subjected to greater repul
sion than the four ligands along +x, -x, +y and -y. This causes tetragonal distortion with four short bonds
and two long bonds. In the same way MnF, contains Mn with a d configuration, and forms a tetragonally
distorted octahedral structure.
Many Cu(+II) salts and complexes also show tetragonally distorted octahedral structures. Cu has a
d' configuration:

To minimize repulsion with the ligands, two electrons occupy the d, orbital and one electron occupies
the d. orbital. Thus the two ligands along -z and -z are repelled more strongly than are the other four
ligands.
The examples above show that whenever the d, and d: orbitals are unequally occupied, distor
tion occurs. This is known as Jahn-Teller distortion. The Jahn-Teller theorem states that Any non-linear
molecular system in a degenerate electronic state will be unstable, and willundergo some sort of distortion
to lower its symmetry and remove the degeneracy.' More simply, molecules or complexes (of any shape
except linear), which have an unequally filled set of orbitals (either ,, or e,), will be distorted. In octahedral
complexes distortions from the t,. level are too small to be detected. However, distortions resulting from
uneven filling of the e, orbitals are very important.