Crystal Field Theory

Bonding in coordination compounds
Nobel prize 1913
Alfred Werner - 1893

VBT
Crystal Field Theory (CFT)
Modified CFT, known as
Ligand Field Theory
MOT
How & Why?
Valance Bond Theory

Basic Principle
A covalent bond forms when the orbtials of two
atoms overlap and are occupied by a pair of
electrons that have the highest probability of
being located between the nuclei.
LinusCarlPauling
(19011994)
Nobelprizes:1954,1962
Valance Bond Model

Ligand = Lewis base
Metal = Lewis acid
s, p and d orbitals give hybrid orbitals with specific geometries
Number and type of M-L hybrid orbitals determines geometry of the complex
Octahedral Complex
e.g. [Cr(NH3)6]3+
Tetrahedral e.g. [Zn(OH)4]2-
Square Planar e.g. [Ni(CN)4]2-
Limitations of VB theory
Cannot account for colour of complexes
May predict magnetism wrongly
Cannot account for spectrochemical series
Crystal Field Theory

400
500
600
The
relationship
between
colors and
complex metal
ions
800
Crystal Field Model

A purely ionic model for transition metal
complexes.
Ligands are considered as point charge.
Predicts the pattern of splitting of d-orbitals.
Used to rationalize spectroscopic and
magnetic properties.
d-orbitals: look attentively along the axis

Linear combination of
dz2-dx2 and dz2-dy2
d2z2-x2-y2
Octahedral Field
We assume an octahedral array of negative charges placed

around the metal ion (which is positive).
The ligand and orbitals lie on the same axes as negative
charges.
Therefore, there is a large, unfavorable interaction between
ligand (-) and these orbitals.
These orbitals form the degenerate high energy pair of
energy levels.
The dxy, dyz, and dxz orbitals bisect the negative charges.
Therefore, there is a smaller repulsion between ligand and
metal for these orbitals.
These orbitals form the degenerate low energy set of energy
levels.
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
Number of ligands and geometry

t< o
t= 4/9 o
Nature of the ligand

I-<S2-<SCN-<Cl-<NO3-<N3-<F-<OH-<C2O42-<H2O<..CN-<CO
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
BEYOND d3
In weak field: O P, => t2g3eg1
In strong field O P, => t2g4
P - paring energy
Ground-state Electronic Configuration,

Magnetic Properties and Colour
Whenthe4thelectronisassigneditwilleithergointothehigher
energyegorbitalatanenergycostofoorbepairedatanenergy
costofP,thepairingenergy.
d4
Strongfield=
Lowspin
(2unpaired)
P < o
P > o
Coulombicrepulsionenergyandexchangeenergy
Weakfield=
Highspin
(4unpaired)
Ground-state Electronic Configuration,

Magnetic Properties and Colour
[Mn(H2O)6]3+
Weak Field Complex
the total spin is 4 = 2
High Spin Complex
[Mn(CN)6]3Strong field Complex
total spin is 2 = 1
Low Spin Complex
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.
What is the CFSE of [Fe(CN)6]3-?

C.N. = 6 Oh
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
CFSE = 5 x - 0.4 oct + 2P = - 2.0 oct + 2P
If the CFSE of [Co(H2O)6]2+ is -0.8 oct, what spin state is it in?

C.N. = 6 Oh
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
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
The magnetic moment of a complex with total

spin quantum number S is:
= 2{S(S+1)}1/2 B ( B is the Bohr magneton)
B = eh/4me = 9.274 10-24 J T-1
Since each unpaired electron has a spin ,
S = ()n, where n = no. of unpaired electrons
= {n(n+2)}1/2 B
In d4, d5, d6, and d7 octahedral complexes,
magnetic measurements can very easily predict
weak versus strong field.
Tetrahedral complexes - only high spin
complexes result, for t O.
n = no. of unpaired electrons

= {n(n+2)}1/2 B
Similar Calculation can be done

for Low-spin Complex
Gouy balance to
measure the magnetic
susceptibilities
The origin of the color of the transition

metal compounds
Ligands influence O, therefore the colour
The colour can change depending on a number of factors

e.g.
1. Metal charge
2. Ligand strength
The optical absorption spectrum of [Ti(H 2O)6]3+

Assigned transition:
eg
t2g
This corresponds to
the energy gap
O = 243 kJ mol-1
absorbed
color
observed
color
Spectrochemical Series: An order of ligand

field strength based on experiment:
Weak Field
I- Br- S2- SCN- Cl-

NO3- F- C2O42- H2O NCS-
CH3CN NH3 en bipy phen
NO2- PPh3 CN- CO Strong Field
H2 N
NH2
N
N
Ethylenediamine (en)
2,2'-bipyridine (bipy)
1.10 - penanthroline (phen)
[CrF6]3-
[Cr(H2O)6]3+
[Cr(NH3)6]3+ [Cr(CN)6]3-
As Cr3+ goes from being attached to a weak field

ligand to a strong field ligand, increases and the
color of the complex changes from green to yellow.
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
Metals in Low Oxidation States

In low oxidation states, the electron density
on the metal ion is very high.
To stabilize low oxidation states, we require
ligands, which can simultaneously bind the
metal center and also withdraw electron
density from it.
Stabilizing Low Oxidation State: CO Can Do the Job
Stabilizing Low Oxidation State: CO Can Do the Job
Ni(CO)4], [Fe(CO)5], [Cr(CO)6], [Mn2(CO)10],

[Co2(CO)8], Na2[Fe(CO)4], Na[Mn(CO)5]
orbital serves as a very weak donor to a metal atom

Crystal Field Theory

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Crystal Field Theory

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Bonding in coordination compounds

Nobel prize 1913

Alfred Werner - 1893

How & Why?

Valance Bond Theory

Valance Bond Model

Tetrahedral e.g. [Zn(OH)4]2-

Square Planar e.g. [Ni(CN)4]2-

Crystal Field Theory

Crystal Field Model

d-orbitals: look attentively along the axis

We assume an octahedral array of negative charges placed

Number of ligands and geometry

Nature of the ligand

Crystal Field Splitting Energy (CFSE)

Ground-state Electronic Configuration,

Ground-state Electronic Configuration,

What is the CFSE of [Fe(CN)6]3-?

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

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

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

The magnetic moment of a complex with total

n = no. of unpaired electrons

Similar Calculation can be done

The origin of the color of the transition

Ligands influence O, therefore the colour

The colour can change depending on a number of factors

The optical absorption spectrum of [Ti(H 2O)6]3+

Spectrochemical Series: An order of ligand

I- Br- S2- SCN- Cl-

1.10 - penanthroline (phen)

As Cr3+ goes from being attached to a weak field

Metals in Low Oxidation States

Stabilizing Low Oxidation State: CO Can Do the Job

Stabilizing Low Oxidation State: CO Can Do the Job

Ni(CO)4], [Fe(CO)5], [Cr(CO)6], [Mn2(CO)10],

orbital serves as a very weak donor to a metal atom

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