Paaras Thakur

Coordination
Compounds 9
1. Jahn Teller distortion
2. Color of complexes

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 Jahn–Teller distortions

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.
 Jahn–Teller distortions

Octahedral complexes of d9 and high-spin d4 ions are often distorted so that two
metal–ligand bonds (axial) are different lengths from the remaining four
(equatorial).
Jahn–Teller distortions

Elongated Octahedron d4 - High Spin

Jahn–Teller distortions

Compressed Octahedron d4 - High Spin

Jahn–Teller distortions
 Crystal field stabilization energy : Octahedral

Why is tetraamminecopper(II) a square planar and not a tetrahedral species?

Color of Transition Metal Complexes
 Color of Transition Metal Complexes

Most transition metal complexes have If we keep the metal constant but vary
beautiful colors that depend on the the ligand, the color also changes.
identity of the metal and the ligands.
 Why we see Color?

When a sample absorbs light, what we

see is the sum of the remaining colors
that strikes our eyes. If a sample absorbs
all wavelength of visible light, none
reaches our eyes from that sample, and
then the sample appears black. If the
sample absorbs no visible light, it is white
or colorless.
 Color of Transition Metal Complexes

The color of a coordination compound is determined by Δ of its complex ion.

Color of Transition Metal Complexes
 Color of Transition Metal Complexes

Energy

1 1 1
1 1 1
[CrF6]3- 1 1 1
Green [Cr(H6O)6]3+ 1 1 1
Violet [Cr(NH3)6]3+
Yellow [Cr(CN)6]3-
Yellow
Example Rank [Ti(H2O)6]3+, [Ti(CN)6]3-, and [Ti(NH3)6]3+ in terms of Δ and of the
energy of visible light absorbed.
 Color of Transition Metal Complexes

Complexes that contain metal ions of d10 electron configuration are usually
colorless. Examples are [Cu(PPh3)4]+ and [Zn(H2O)6]2+. One would expect a
metal complex with no d-electron to be colorless as well.

However, a few of such complexes are strongly colored, for example, MnO4- or
[Cr2O7]2-.

The origin of the color in these complexes is not the d-d transitions, rather due to
‘charge transfer’
 Color of Transition Metal Complexes
Charge Transfer Bands
LMCT
● e.g. Transfer of an electron
from p-orbital on a chloride
(u symmetry) to a metal’s d-
orbital (g symmetry).
● Favourable when metal centre
is in high oxidation state.
● Common for π-donor ligands
(F-,O2-, N3-, OH-)
● e.g. Colour of KMnO4
(d0 complex)
MLCT
● e.g. Transferred of electron
from metal’s π* orbital to
orbital of CO ligand
● Favoured electron rich metal
centres and those ligated by
π- acceptors
● Often higher in energy (in the
UV region)
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