NPTEL – Chemistry and Biochemistry – Coordination Chemistry (Chemistry of transition

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Coordination Chemistry: Bonding

Valence Bond Theory & Crystal Field Theory

K.Sridharan

Dean

School of Chemical & Biotechnology

SASTRA University

Thanjavur – 613 401

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Table of Contents
Valence Bond Theory and Crystal Field Theory ............................................................................... 3
1.1 Valence bond theory ............................................................................................................. 3
1.1.1 Hybridization and shape ..................................................................................................... 3
1.1.2 Correlation between the observed magnetic property and structure .............................. 4
2. Crystal Field Theory ..................................................................................................................... 9
2.1 Postulate ................................................................................................................................ 9
2.2 Shapes of d-orbitals ............................................................................................................... 9
2.2.1Shape of dz2 orbital is different. Why?............................................................................ 9
2.2.2 Degeneracy of d-orbitals .............................................................................................. 10
2.3 Crystal field effects .............................................................................................................. 11
2.3.1 Octahedral symmetry ................................................................................................... 11
2.3.2 Measurement of Δ o : [Ti(H 2 O) 6 ]3+ ................................................................................. 13
2.3.3 Crystal field stabilization energy (CFSE) ....................................................................... 15
2.3.4. Splitting in d2 and d3 metal ions .................................................................................. 16
2.3.5 Electron pairing energy (P) ........................................................................................... 18

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Valence Bond Theory and Crystal Field Theory

1.1 Valence bond theory
According to this theory, coordinate bond is formed between Lewis bases, which
are called ligands, and the Lewis acids, which are nothing but the metal ions.
Ligands are called Lewis bases because they donate lone pair of electrons and
metal ions are called Lewis acids because they accept lone pair of electrons.
E.g. [Co(NH3) 6 ]3+
In this complex, the metal ion is Co3+ and NH 3 is the ligand.

NH3 Co3+ H3N Co

Lewis Lewis
base acid

The metal s, p, d and f orbitals hybridize and the hybridized orbitals are used for
bond formation. The shape of the complex formed depends up on the nature of
hybridization and also the magnetic properties.

1.1.1 Hybridization and shape

The different types of hybridizations and the corresponding shapes are given
below:

Hybridization Shape
sp3 Tetrahedral
dsp2 Square planar
sp3d2 or d2sp3 octahedral
L L
L L L
L
L M M
L L L L L
L
L
Tetrahedral Square planar Octahedral

M – metal ion; L - ligand

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1.1.2 Correlation between the observed magnetic property and

structure
Pd(II) and Pt(II) are usually four coordinate, square planar and diamagnetic. How
to explain this with the help of valence bond theory?
If a compound is paramagnetic, it will have unpaired electrons and if the
compound is diamagnetic, all the electrons will be paired.
Example 1:
Let us consider the complex, [PtCl 4 ]2-. This complex is square planar and
diamagnetic.
The oxidation state of Pt in this complex is +2.
Outermost electronic configuration of Pt atom is 5d86s2
Electronic configuration of Pt2+ ion is 5d8; there are five .d. orbitals and the 8
electrons are arranged as follows:

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d s p

dsp2 hybridization
Each Cl- will donate a pair of electrons to the vacant orbitals as shown by ‘X’
mark.

Cl Cl Cl Cl
As seen above, all the electrons are paired and hence, the complex is
diamagnetic.

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Example 2: [NiCl 4 ]2-

This complex is paramagnetic. That is, it has got unpaired electrons. Valence
bond theory can explain this as follows:
Outermost electronic configuration of Ni atom is 3d84s2

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Outermost electronic configuration of Ni2+ is 3d8 and these are arranged in the
five .d-orbitals as follows:

sp3
Thus there are two unpaired electrons in the .d. orbitals. Hence, the complex will
be paramagnetic. The hybridization is sp3 as shown. Therefore, the shape of the
complex will be tetrahedral.

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In these examples, the hybridization and shape are decided by the magnetic
property of the complex. Thus, it is called .magnetic criterion of bond type.

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Example 3: [CoF 6 ]3-

This complex is paramagnetic.and this is explained by VBT as follows:
Outermost electronic configuration of Co is: 3d74s2
Cobalt is in the +3 state in this complex. Therefore, the outermost electronic
configuration of Co3+ is 3d6. Since the complex is paramagnetic, the electrons are
arranged as follows and there are four unpaired electrons.

sp3d2
The hybridization is sp3d2 and the shape is octahedral.

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Example 4: [Co(NH 3 ) 6 ]3+

This complex is diamagnetic and explained by VBT as follows:
Outermost electronic configuration of Co is: 3d74s2
Cobalt is in the +3 state in this complex. Therefore, the outermost electronic
configuration of Co3+ is 3d6. Since the complex is diamagnetic, the electrons are
arranged as follows:

d2sp3
There are no unpaired electrons and hence, the complex is diamagnetic. The
hybridization is d2sp3 and the shape is octahedral.

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2. Crystal Field Theory

2.1 Postulate
The interaction between the ligands and metal ions are considered to be purely
electrostatic and the ligands are considered to be point negative charges.

2.2 Shapes of d-orbitals

The shapes of the five d-orbitals are given in Figure 2.2.1.

x z
y

y x

z
dz2
dx2-y2

y z z

x y x

dx y dyz dzx

Fig 1 Shapes of d-orbitals

2.2.1Shape of dz2 orbital is different. Why?

Actually, d z 2 orbital is a linear combination of two orbitals, namely,
d z2-x2 and d z2-y2. This is shown in Figure 2.2.1.1.

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z z
y z
y
y
x + x x

dz2
dz2-x2 dz2-y2

Fig 2.2.1.1 Formation of d z2 orbital

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2.2.2 Degeneracy of d-orbitals

All the five d-orbitals are degenerate (same energy) in the isolated, gaseous
metal ion. When they are surrounded by spherically symmetric field of negative
charges, the orbitals are raised in energy because of the repulsion between like
charges but still they are degenerate. However, in the real case, the number of
ligands surrounding the metal ion may be eight or so. Now, the field is not
spherical and has lower symmetry. Therefore, the five d-orbitals are no longer
degenerate and are split.
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2.3 Crystal field effects

When the metal ion is surrounded by the ligands, there is repulsion between the
ligand electrons and metal d-electrons. This is called crystal field effect. This can
be considered for different symmetries, viz., octahedral symmetry, tetrahedral
symmetry, tetragonal symmetry and other symmetries.

2.3.1 Octahedral symmetry

In this case six ligands coordinate to the metal ion and form an octahedral
complex. The six ligands are approaching along the coordinate axes and hence
the five .d.orbitals are raised in energy because of the electron-electron
repulsion. However, all the d-orbitals are not raised in energy to the same extent.
Those orbitals whose lobes point along the axes are raised in energy very much,
while the other d-orbitals are raised in energy to a lesser extent. The reason is
that the ligands considered being spheres approach along the axes. Thus, the
five d-orbitals are split into two groups: the dx2-y2 and d z2 orbitals form one set,
while the other three orbitals, d xy , d yz and d zx form another group. The former are
known as e g (doubly degenerate) orbitals and the latter are known as t 2g (triply
degenerate) orbitals. These are shown in Figure 2.3.1.1

eg

E
+6Dq

10Dq = ∆0

-4Dq
x2-y2 z2 xy yz zx
t2 g

Fig 2.3.1.1 Splitting of d-orbitals

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During splitting, the centre of gravity rule is obeyed. That is,2 orbitals (+6Dq) + 3
orbitals (-4Dq) = 0. In Δ 0 , subscript .o. stands for octahedral.

The approach of ligands with respect to d x2-y2 and d z2 orbitals is shown in Figure
2.3.1.2 and the approach with respect to d xy orbital is shown Figure 2.3.1.3.

Fig 2.3.1.2 Ligands approaching the e g orbitals

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z
y

Fig 2.3.1.3 Ligands approaching the t 2g orbitals

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2.3.2 Measurement of Δo: [Ti(H2O)6]3+

This aqueous solution of this complex gives a purple color. This is explained as
follows.Titanium exists as Ti3+ in the complex and has a single .d. electron. This
single electron in.the complex occupies the lowest energy level available,
namely, one of the degenerate t 2g orbitals. This electron absorbs energy and is
excited to the e g level. This absorbed energy appears as pink color. This
transition is denoted as t 2g 1e g 0 t 2g 0e g 1.

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t 2g 1e g 0 t 2g 0e g 1

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The absorption spectrum of hexaaquotitanium(III) ion is shown in

Figure 2.3.2.1.

20300 cm-1
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Fig 2.3.2.1.Absorption spectrum of Ti(H 2 O) 6 3+

The spectrum shows that maximum absorption takes place at 20300 cm-1 which
is in the green region of the visible spectrum. Hence, its complimentary color,
pink, is emitted and the solution appears pink. Hence, Δ 0 = 20,300 cm-1 for this
complex.

2.3.3 Crystal field stabilization energy (CFSE)

In the above example, the single .d. electron in the complex is stabilized
compared to the free ion or spherical field. The reason is that in the free ion or
spherical field, the five d orbitals were degenerate and were having higher
energy, while in the octahedral complex, the d orbitals split into two groups, viz.,
t 2g and e g . The t 2g orbitals have lower energy of -0.4 Δ 0 compared to the
barycenter of the d-orbitals. This is called CFSE. This is schematically shown in
Figure 2.3.3.1.

+0.6 Δo

-0.4 Δo

Fig 2.3.3.1 CFSE

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2.3.4. Splitting in d2 and d3 metal ions

Hund’s rule is obeyed and hence the two electrons in d2 remain unpaired in the
two of the three t 2g orbitals. Similarly, in the d3 case, the three electrons will
occupy the three degenerate t 2g orbitals. Then the CFSE is calculated as follows:
d2 system:

+0.6 Δo CFSE = 2(-0.4 Δ o ) + 0(+0.6 Δ o )

= -0.8 Δ o
-0.4 Δo

d3 system:

CFSE = 3(-0.4 Δ o ) + 0(+0.6 Δ o )

= -1.2 Δ o

2.3.4.1 Strong and weak field case

d4 system:

Here, there are two possibilities, viz., the 4th electron can go to the e g orbital or it
can pair with the electrons in the t 2g orbitals. It depends up on the magnitude of
the splitting of the d-orbitals.

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Case 1: P < Δ 0
If the splitting of the d-orbitals is more, then Δ 0 will be more and the e g orbitals
will have very high energy. Now, the 4th electron cannot go to the e g orbitals but
will remain paired in the t 2g orbitals. The pairing energy (P), that is, the energy
required to overcome the repulsion between electrons during pairing, P, is less
than Δ 0 .(P < Δ 0 ). This is called a strong field case.
Case 2: P > Δ 0
Here the splitting will be less and the pairing energy will be greater than the
energy of the e g orbitals. Therefore, the electrons will go to the e g orbitals rather
than going to the t 2g orbitals. This is called a weak field case.
These are schematically shown below:

Δo

P < Δo P > Δo

(Strong field) (Low-spin) (Weak-field) (High-spin)

Splitting is more Splitting is less

CFSE = 4(-0.3 Δ o ) = -1.2 Δ o CFSE = -1.2 +0. 6 = -0.6 Δ o

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In this manner, CFSE for the dn systems can be calculated and is given in Table
2.3.4.1.1.
Table 2.3.4.1.1 CFSE of dn systems

dn Weak field Strong field

Configuration CFSE No of Configuration CFSE No of
Δo unpaired Δo unpaired
electrons electrons
d1 t 2g 1e g 0 -0.4 1 t 2g 1e g 0 -0.4 1
d2 t 2g 2e g 0 -0.8 2 t 2g 2e g 0 -0.8 2
d3 3
t 2g e g 0
-1.2 3 3
t 2g e g 0
-1.2 3
d4 t 2g 3e g 1 +0.6 4 t 2g 4e g 0 -1.6 2
d5 3
t 2g e g 2
0 5 5
t 2g e g 0
-2.0 1
d6 t 2g 4e g 2 -0.4 4 t 2g 6e g 0 -2.4 0
d7 5
t 2g e g 2
-0.8 3 6
t 2g e g 1
-1.2 1
d8 6
t 2g e g 2
-1.2 2 6
t 2g e g 2
-1.2 2
d9 t 2g 6e g 3 -0.6 1 t 2g 6e g 3 -0.6 1
d10 6
t 2g e g 4
0 0 6
t 2g e g 4
0 0

Δ 0 = 10Dq; -0.4Δ o or -4Dq

2.3.5 Electron pairing energy (P)

Let us consider d6 low-spin configuration, t 2g 6e g 0

CFSE = 24Dq - 3P

Let us consider d6 high-spin configuration, t 2g 4e g 2

CFSE = 16Dq - P

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2.3.5.1 Composition of electron pairing energy

This is composed of two terms:
1. Inherent coulombic repulsion
This is the repulsion when two electrons occupy the same orbital. This repulsion
decreases when the atomic size increases within a group when we go from top to
bottom. The orbitals become bigger and diffuse so that the distance between the
two electrons in the orbitals decreases and hence the repulsion decreases. Thus
5d orbitals are more diffuse than the 3d orbitals and hence electrons can be
easily accommodated in the 5d orbitals. This repulsion must be overcome when
two electrons are forced to occupy the same orbital.
2. Loss of exchange energy
This occurs when electrons having parallel spins are forced to have antiparallel
spins. The exchange energy is proportional to the number of pairs of electrons
(set of two electrons) having parallel spins. Thus the greatest loss of exchange
energy occurs when the d5 configuration (Mn2+ and Fe3+) is forced to pair.
Therefore, d5 complexes are usually high spin complexes.

3 References
1. “Inorganic Chemistry: Principles of Structure and Reactivity”, James
E.Huheey, Ellen A.Keiter, Richard L.Keiter, Okhil K.Medhi, Pearson
Education, Delhi, 2006

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