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Crystal Field Theory
Crystal Field Theory
LinusCarlPauling
(19011994)
Nobelprizes:1954,1962
Octahedral Complex
e.g. [Cr(NH3)6]3+
Limitations of VB theory
Cannot account for colour of complexes
May predict magnetism wrongly
Cannot account for spectrochemical series
500
600
The
relationship
between
colors and
complex metal
ions
800
Octahedral Field
In Octahedral Field
yz
xz
z2
x2-y2
d
xy
In Tetrahedral Field
Magnitude of
Oxidation state of the metal ion
[Ru(H2O)6]2+
19800 cm-1
[Ru(H2O)6]3+
28600 cm-1
t= 4/9 o
BEYOND d3
In weak field: O P, => t2g3eg1
In strong field O P, => t2g4
P - paring energy
Whenthe4thelectronisassigneditwilleithergointothehigher
energyegorbitalatanenergycostofoorbepairedatanenergy
costofP,thepairingenergy.
d4
Strongfield=
Lowspin
(2unpaired)
P < o
P > o
Coulombicrepulsionenergyandexchangeenergy
Weakfield=
Highspin
(4unpaired)
Placingelectronsindorbitals
d5
1u.e.
5u.e.
d6
0u.e.
4u.e.
d8
2u.e.
2u.e.
d7
1u.e.
3u.e.
d9
1u.e.
1u.e.
d10
0u.e.
0u.e.
Fe(III) d5
3-
CN
NC
Fe
NC
h.s.
l.s.
eg
CN
CN- = s.f.l.
eg
+ 0.6 oct
CN
CN
- 0.4 oct
t2g
t2g
Co(II) d7
OH2
H 2O
Co
H 2O
OH2
2+
h.s.
l.s.
eg
eg
+ 0.6 oct
OH2
OH2
t2g
t2g
- 0.4 oct
Gouy balance to
measure the magnetic
susceptibilities
t2g
This corresponds to
the energy gap
O = 243 kJ mol-1
absorbed
color
observed
color
H2 N
NH2
N
N
Ethylenediamine (en)
2,2'-bipyridine (bipy)
[CrF6]3-
[Cr(H2O)6]3+
[Cr(NH3)6]3+ [Cr(CN)6]3-
Limitations of CFT
Considers Ligand as Point charge/dipole only
Does not take into account of the overlap of ligand and
metal orbitals
Consequence
e.g. Fails to explain why CO is stronger ligand than CN- in
complexes having metal in low oxidation state