Crystal Field Theory

1. This is an electrostatic model for transition metal complexes.

2. Ligands are considered as point charge.
3. The CFT does not provide for electrons to enter the metal orbitals, i.e. it does not
consider any orbital overlap.
4. Predicts the pattern of splitting of d-orbitals.
5. Used to rationalize spectroscopic and magnetic properties.

Octahedral complex (Oh) Tetrahedral complex (Td) Square planer complex (Sp)
 Octahedral Field
• Six point negative charges (Ligands)
representing the ligands are placed in an
octahedral array around the central metal
ion.
• The ligand and orbitals lie on the same
axes.
• These charges interact strongly with the
central metal ion.

1. The stability of the complex in large 2. There is a much smaller but very
part from this attractive interaction important secondary effect arising from
between opposite charges. the fact that electrons in different d
orbitals interact with the ligands to
different extents.
 Although this differential interaction is little
more than about 10 per cent of the overall
metal-ligand interaction energy, it has
major consequences for the properties of
the complex.
Octahedral Field
 Octahedral Field

dyz

dz 2

dxz

dx2-y2

dxy
Splitting of d-orbital energies in an octahedral field of ligands.

The d orbitals split into two groups. The difference in energy

between these groups is called the crystal field splitting energy,
symbol Δo.
 Octahedral Field

Barycentre

• The overall stabilization of the t2g orbitals equals the overall

destabilization of the eg set.

• Thus, the two orbitals in the eg set are raised by 0.6 Δo with respect to
the Barycentre while the three in the t2g set are lowered by 0.4 Δo.

• The magnitude of Δo is determined by the strength of the crystal

field, the two extremes being called weak field and strong field.

Δo (Weak field) < Δo (Strong field)

 Factors influencing the Magnitude of o for Octahedral complexes

1. The nature of metal cation:

i) Oxidation state of the metal ion
[Ru(H2O)6]3+ 28600 cm-1
[Ru(H2O)6]2+ 19800 cm-1
ii) Different charges on the cation of different metals
[V(H2O)6]2+ 12400 cm-1 3d3
[Cr(H2O)6]3+ 17400 cm-1 3d3
iii) Quantum number (n) of the d- orbitals of the central metal ion.
[Co(NH3)6]3+ 23000 cm-1 3d6
[Rh(NH3)6]3+ 34000 cm-1 4d6
[Ir(NH3)6]3+ 41000 cm-1 5d6

o increases about 30% to 50% from 3dn to 4dn. And by about

same amount again from 4dn to 5dn. The increase down a group
reflects the larger size of the 4d and 5d orbitals compared with the
compact 3d orbitals and the consequent stronger interactions with
the ligands.
 Strong and weak ligands: Spectrochemical Series

Weak Field I-  Br- S2- SCN- Cl- NO3- F-  C2O42-

H2O NCS- CH3CN NH3 en  bipy phen NO2-
 PPh3 CN- CO
Strong Field
 Crystal Field Splitting Energy (CFSE)
• In Octahedral field, configuration is: t2gx egy
• Net energy of the configuration relative to the average energy
of the orbitals is:
= (-0.4x + 0.6y)O
O = 10 Dq

d1
Crystal Field Splitting Energy (CFSE)

d2 Ti2+, V3+

d3 Cr3+, Mn4+,V2+
When the 4th electron is assigned it will either go into the higher
energy eg orbital at an energy cost of o or be paired at an energy cost
of P, the pairing energy.

d4

Strong field = Weak field =

Low spin High spin
(2 unpaired) (4 unpaired)

P < o P > o
Coulombic repulsion energy and exchange energy
Crystal Field Splitting Energy (CFSE)

[Mn(H2O)6]3+
Weak Field Complex
the total spin (S) is 4  ½ = 2
High Spin Complex

Weak field d4

[Mn(CN)6]3-
Strong field Complex
total spin (S) is 2  ½ = 1
Low Spin Complex

Strong field d4
 Placing electrons in d orbitals
d5 d6 d7

1 u.e. 5 u.e. 0 u.e. 4 u.e. 1 u.e. 3 u.e.

d8 d9 d10

2 u.e. 2 u.e. 1 u.e. 1 u.e. 0 u.e. 0 u.e.

What is the CFSE of [Fe(CN)6]3-? CN- = S.F.L.
C.N. = 6  Oh Fe(III)  d5 H.S. L.S.
CN 3-
eg eg
CN
NC
Fe + 0.6 oct
NC CN
- 0.4 oct
CN t2g
t2g

CFSE = 5 x - 0.4 oct + 2P = - 2.0 oct + 2P

If the CFSE of [Co(H2O)6]2+ is -0.8 o, what spin state is it in?

C.N. = 6  Oh Co(II)  d7 H.S. L.S.

2+ eg eg
OH2
+ 0.6 oct
H2O OH2
Co - 0.4 oct
H2O OH2 t2g t2g
OH2
CFSE = (5 x - 0.4 oct) CFSE = (6 x - 0.4 oct)
+ (2 x 0.6 oct) +2P = - 0.8 oct+2P + (0.6 oct) + 3P= - 1.8 oct + P
Crystal Field Splitting Energy (CFSE)