CRYSTAL FIELD THEORY

DR KARIMAH KASSIM
 Bonding in Octahedral Coordination Compounds

Isolated
transition metal
atom Crystal field splitting diagram
for an octahedral complex

Crystal field splitting ( D) is the energy difference between

two sets of d orbitals in a metal atom when ligands are present
Bonding in Coordination Compounds

DE = hn

5
 Bonding in Coordination Compounds

Spectrochemical Series

I- < Br- < Cl- < OH- < F- < H2O < NH3 < en < CN- < CO

Weak field ligands Strong field ligands

Small D Large D 6
 Magnitude of D
1) Depends on oxidation state of metal
ion
– Higher oxidation state produces large D
2) Depends on nature of metal ion
– Metals further down the periodic table
produces large D
3) Depends on the type of ligand
– A strong field ligand produces a large D
– A weak field ligand produces a small D
3. Nature of ligands
eg

eg
Doct
Doct I- < Br- < S2- < SCN- ≈ Cl-< NO3- < F- < OH- < ox2-

t2g < H2O < NCS- < CH3CN < NH3 ≈ en < bpy

< phen ≈ NO2- < PR3 < CN- ≈ CO

Weak Field Ligands
High Spin Complexes

t2g

Strong Field Ligands

Low Spin Complexes

The Spectrochemical Series

 Colors of Some Transition Metal Ions

Ti3+ Cr3+ Mn2+ Fe3+ Co2+ Ni2+ Cu2+

12
 Figure 23.15 An artist’s wheel.
Copyright  The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

Each color has a complementary

color; the one opposite it on the
artist’s wheel.

The color an object exhibits depends

on the wavelengths of light that it
absorbs.

An object will have a particular color because

• it reflects light of that color, or
• it absorbs light of the complementary color.
Table 23.9 Relation Between Absorbed and Observed Colors

Absorbed Color l (nm) Observed Color l (nm)

Violet 400 Green-yellow 560

Blue 450 Yellow 600
Blue-green 490 Red 620
Yellow-green 570 Violet 410
Yellow 580 Dark blue 430
Orange 600 Blue 450
Red 650 Green 520
 Figure 23.22 The spectrochemical series.

•For a given ligand, the color depends on the oxidation state of the metal ion.

•For a given metal ion, the color depends on the ligand.

I- < Cl- < F- < OH- < H2O < SCN- < NH3 < en < NO2- < CN- < CO

WEAKER FIELD STRONGER FIELD

SMALLER D LARGER D

LONGER l SHORTER l
HS and LS for Octahedral d4, d5, d6 and d7

Cr2+

Mn2+,
Fe3+

Fe2+,
Co3+

Co2+
Bonding in Tetrahedral Coordination Compounds
 Tetrahedral Complexes

• Will almost always be high spin

regardless of the ligand because the
size of D is small for tetrahedral
complexes.

D tet = 4/9(Doct)