Crystal Field Theory

Proposed by Bethe and van Vleek.

The ligands are considered as point charges.
The interaction between metal and ligand is

purely electrostatic i.e. bonding is due to ionion attraction if ligand is ionic or ion-dipole
attraction if ligand is neutral.
Explain reasonably the electronic spectra and
magnetism of the transition metal complexes.

CFT views the metal orbitals

are in presence of external
field created by the Ligands.

d-orbitals in external field

Free metal ion

(no field)

Like in the isolated metal, the dorbitals of metal in a spherically

symmetric field are degenerate,

however, the average energy
increases.

What happen to
the d-orbitals in
an Octahedral
field ?

d-orbitals in Octahedral field

In these orbitals (e-type),
the ligands point right at
the lobes; Interact strongly

In these orbitals (t2-type), the ligands are between the lobes;

Interact less strongly

d-orbitals in external field

Free metal ion

(no field)

Octahedral field

Splitting due to
ligand/orbirtal orientation

CFT - Octahedral Complexes

The gap in the d orbitals is assigned a value of 10Dq or 0. As the
baricenter must be conserved on going from spherical to octahedral
field, the t2 set must be stabilized as much as the e set is
destabilized.

CFSE (0.4 nt2 g 0.6 neg ) O

The actual size of the gap varies with the metal and the
ligands.

Splitting of d-orbitals

The colors exhibited by most transition metal complexes

arises from the splitting of the d orbitals whose SPACING
corresponds to the wavelength of light available in visible
region (complimentary color is observed).
The splitting can be measured using a spectrophotometer.

Crystal Field Stabilization Energy (CFSE)

1. o increases with increasing oxidation number on the

metal.
Mn+2<Ni+2<Co+2<Fe+2<V+2<Fe+3<Co+3
<Mn+4<Mo+3<Rh+3<Ru+3<Pd+4<Ir+3<Pt+4
2. o increases with increases going down a group of
metals.

3. Crystal field splitting of

various ligands with same
metal ion

Spectrochemical Series

Smaller o
colors in the
green range;
Larger o :
Yellow color

The complexes of cobalt (III) show the shift in color due to the ligand.
(a) CN, (b) NO2, (c) phen, (d) en, (e) NH3, (f) gly, (g) H2O, (h) ox2, (i) CO3 2.

Spectrochemical series (strength of ligand interaction)

Increasing

Cl- < F- < H2O < NH3 < en < NO2- < CN-

Increasing

As the splitting increases, electron configuration might change;

Co(III) is d6

High spin
or
Weak Field

Low spin or Strong Field

When > P (pairing energy), pairing of electrons takes place resulting

low spin complexes:

CFSE & electronic arrangements in octahedral complexes

Note:
Total stabilization
energy = CFSE + Total
Pairing energy
CFSE
(0.4 nt2 g 0.6 neg ) O

Possibility of both low

& high spin complexes

Symmetrical electron
arrangement:
d0, d3, d5(w), d6(s), d8,
d10

Effects of Crystal Field Splitting

Lattice Energy (U):
M+ (g) + X- (g) MX (s)

Many transition metal

complexes have a higher
measured (Born-Haber)
lattice energy than
calculated (Born-Linde)
value.

do

CFSE

d1

d2

d3

d4

d5 d6

d7

d8

d9

d10

0 .4o

.8

1.2

.6

0 .4

.8

1.2

.6

Effects of Crystal Field Splitting

Hydration Energy: M2+ + 6 H2O(l) M(H2O)62+

The hydration energies of

the first row transition
metals should increase
across the period as the
size of the metal ion gets
smaller.

do d1 d2
CFSE 0 .4o .8

d3
1.2

d4 d5 d6 d7 d8
.6 0 .4 .8 1.2

d9 d10
.6 0

Effects of Crystal Field Splitting

Variation of ionic radii of M2+ ions:
Electrons in t2g orbitals are
away from ligands, so less
shielding (size decreases).

Tetragonal distortion of octahedral complexes

(Jahn-Teller Distortion)
Shape of metal complex is determined by the tendency of electron pairs to
occupy positions as far away from each other as possible
If asymmetrically filled some ligands are repelled more than the other.
Result: Distorted octahedron
Any non-linear molecular system in a degenerate
electronic state will be unstable, and will undergo
distortion to lower its symmetry & remove the
degeneracy Jahn Teller theorem

X
Y

(e.g. d9 system)
&

T2(6)+Eg(2)

Electron in dz2 orbital will be

Repelled by only two ligands,
But that of dx2-y2 will be
repelled by four ligands.

d x2 y 2

d z2

Square-Planner complexes

Tetrahedral Field

Tetrahedral
Complex

Example Problems
1. Calculate CFSE for [Cr(H2O)6]2+. Given P = 23500 cm-1 and =
13900 cm-1. What will be CFSE for low spin configuration?
2. Enthalpy of hydration of Cr2+ is -460 kcal/mol. In absence of
CFSE, the value of H is -435 kcal/mol. Estimate for [Cr(H2O)6]2+.

3. Draw a crystal field splitting diagram for a complex in a linear

field, assume that the ligands lie along Z-axis.
4. A certain metal ion M2+ forms the following complexes:
[M(H2O)6]2+, [M(Br)6]4-. [M(en)3]2+.
If the color of the complexes are green, red and blue, match the
complexes with appropriate color & explain.