Valence Bond Theory (VBT)

Introduction
We have already said that Werner was the first to explain the
nature of bonding in complex compounds. However, with the
advancement of theories of valence, modern theories have been
proposed to explain the nature of metal-ligand bonding in complexes.
These theories can also explain the colour, geometry and magnetic
properties of the complex compounds. These mode theories are:
(i) Valence Bond Theory: VBT (due to L. Pauling and JL Slater, 1935)
(ii) Crystal Field Theory: CFT (due to H. Bethe. 1929 and Van Vleck,
1932) (iii) Ligand Field Theory LFT or Molecular Orbital Theory, MOT
(due to J. Van Vleck, 1935). Here we shall discuss only valence bond
theory.
♦

Valence Bond Theory (VBT)

This theory is mainly due to Pauling. It deals with the electronic
structure of the central metal ion in its ground state, kind of bonding,
geometry and magnetic properties of the complexes.

Assumptions of valence bond theory :

1. The central metal atom or ion makes available a number empty s, p
and d atomic orbitals equal to its coordination number. These vacant
orbitals hybridized together to form hybrid orbitals which are the same in
number as the atomic orbitals hybridized together. These hybrid orbitals
are vacant, equivalent in energy and have definite geometry: Important
types of hybridisation occuring in the first row transition metal (3d)
complexes and the geometry of the complex are given in Table.

2. The ligands have at least one u-orbital containing a lone pair of

electrons.

3. Vacant hybrid orbitals of the metal atom or ion overlap with the filled
(containing lone pair of electrons) u-orbitals of the ligands to form
ligand---+ metal u-bond. This bond is known as coordinate bond is a
special type of covalent bond and shows the characteristics of both the

Dr. Trupti Darji (V.P. and R.P.T.P. Science College) 1

 Coordination Type of hybridisation Geometry of the Examples of complexes
number of the undergo11e by the central complex.
central metal metal atom/ion
atom/ion

2 sp(4s, 4px) Linear or [CuCl2J-, [Cu(NH3h]"'" etc.

< :J::H
diagonal

3 sp2(4s, 4px, 4p ) Trigonal planar

1
or equilateral
triangular [CuiS=C
[Cu+Cl(tu)i]11 (distorted trigonal
planar) etc.
2
4 dsp2(3di-l, 4s, 4px, 4p1) Square planar [Ni(C )4] -, [PdCLiJ2-

4 sp2d(4s, 4p_., 4p1, 4d,x2 _y1) Square planar [Cu(NH3)4]2+

[Pt(NH1)4)2+ etc.

4 si1(4s, 4p.., 4p , 4p,) Tetrahedral [NiC'4]2 , [Cu(CN)4]3-, Ni(C0)4

1
etc.

5 dsp3(3dz1, 4s, 4px, 4py, 4pz) Trigonal Fe(C0)5, [CuC15]1-,

bipyramidal [Ni2+(triars) Br2)0

5 dsp1(3dx'-y', 4s, 4px, 4p1,

4pJ
Square pyramidal [Co2-t-(triars) 12]0• [Ni(CN)5] -
gr
6 dl,sp3(3d,t2-y', 3d;, 4s, 4p.,,
4py, 4pJ
Inner-orbital
octahedral
M
etc.

[Ti(H20)6]3+, [Fe(CN)6]3- etc.

6 sp3tf (4s, 4p.i, 4p1, 4p,., Ou!er-orbital
4d..J-l, 4dz1) octahedral
This octahedral geometry arises due to d 2sp3 or sp3d2 hybridisation of the central
metal atom or ion. What type of hybridisation will occur depends on the number
of unpaired or paired electrons present in the complex ion. d2sp3 or sp3d2
hybridisation is also called octahedral hybridisation.

Octahedral complexes in which the central atom is d2sp3

hybridised are called inner-orbital octahedral complexes while the
octahedral complexes in which the central atom is sp3d2 hybridised are
called outer-orbital octahedral complexes.

d2sp3 Hybridisation in Inner Orbital Octahedral Complexes:

This type of hybridisation takes place in those octahedral

complexes which contain strong ligands. On the basis of the orientation
of the lobes of d-orbitals in space, these orbitals have been classified
into two sets viz. t29 (dxy, dyz and dxz) and e9 (dz2and dx2-y2) orbitals. In the
formation of six d2sp3 hybrid orbitals, two (n-1) d-orbitals of e 9 set, one ns
and three np (npx, npy, and npz) orbitals combine together and form six
d2sp3 hybrid orbitals.
Thus we see that the two d-orbitals used in d 2sp3 hybridisation are
from penultimate shells [ie. (n-1)th shell] while s and three p-orbitals are
from ultimate shell (ie. nth shell). This discussion shows that in case of
octahedral complex ions of 3d transition series elements, two d-orbitals
used in d2sp3 hybridisation are 3dz2 and 3dx2-y2 orbitals while s- and
p-orbitals are 4s and 4p orbitals. Thus d2sp3 hybridization taking place in
such complexes can be represented as: dx2-y2.dz2.4s.4px.4py.4pz{d2sp3).
Since two d-orbitals used in d2sp3 hybridisation belong to the inner
shell [i.e. (n-1)th shell], the octahedral complex compounds resulting
from d2sp3 hybridisation are called inner orbital octahedral complexes.

Ferrocyanide ion OR hexacyanoferrate (II) ion [Fe(CN)6]4· :

In this ion, since the coordination number of Fe is six, the given

complex ion has octahedral geometry. In this ion, Fe is present as Fe2+
ion whose valence-shell configuration is 3d6 4s0 4p0 or , t294 e9 24s0 4p0
which shows that Fe2+ ion has 4 unpaired electrons. Magnetic studies

Dr. Trupti Darji (V.P. and R.P.T.P. Science College) 3

have, however, shown that the given complex ion is diamagnetic and
hence it has no unpaired electrons (n = 0). Hence in order to get all the
electrons in the paired state, two electrons of eg orbitals are sent to t2g
orbitals so that n becomes equal to zero.
Since CN- ions (ligands) are strong ligands, they are capable of
forcing the two electrons of eg orbitals to occupy t2g orbitals and thus
make all the electrons paired. Now for the formation of [Fe(CN)6]4- ion,
two 3d orbitals of eg set, 4s orbital (one orbital) and three 4p orbitals (all
these six orbitals are vacant orbitals) undergo d 2sp3 hybridisation (see
Figure). It is due to d2sp3 hybridisation that [Fe(CN)6]4- ion is an inner
orbital octahedral complex ion. The electron pair donated by CN- ion
(ligand) is accommodated in each of the six d2sp3 hybrid orbitals as
shown in Figure.

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Dr. Trupti Darji (V.P. and R.P.T.P. Science College) 4
e
[Fe(CN)6]3- ion) and s and p orbitals are 4s and 4p. Thus the given ion
results from (4s) (4p3) (4dz2) (4dx2-y2) hybridisation as shown in Figure. This
discussion shows that in the formation of [FeF6]3- in the original valence-
shell configuration of Fe3+ ion is not disturbed.

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Dr. Trupti Darji (V.P. and R.P.T.P. Science College) 6
 Differences between inner orbital and outer orbital
octahedral complexes

Inner orbital octahedral Outer orbital octahedral

complexes complexes

(i) These are formed by d2sp3 (i) These are formed by sp3d2
hybridisation i.e.in the formation of hybridisation i.e.in the formation of
six d2sp3 hybrid orbitals, two six sp3d2 hybrid orbitals, two nd
(n-1)d orbitals of e 9 set, one ns orbitals of e 9 set, one ns and three
and three np orbitals are used. np orbitals are used. Thus all the
(n-1)d orbitals belong to the inner orbitals belong to the outer
(penultimate) shell while ns and (ultimate) shell.
np orbitals belong to the outer
(ultimate) shell.

(ii) These complexes have (ii) These complexes have a

comparatively lesser number of comparatively greater number of
unpaired electrons and hence are unpaired electrons and hence are
also called low spin or spin paired also called high spin or spin free
complexes. complexes.

(iii) These are given by strong (iii) These are given by weak
ligands. ligands.
♦

Geometry of 4-coordinate complex ions :

Examples of 4-coordinated complex ions formed by some

transition metals. In these complex ions the coordination number of the
central metal atom or ion is four. Such complex ions may have either
square planar or tetrahedral geometry, depending on whether the central
atom or ion is dsp2 or sp3 hybridised. What type of hybridisation (ie..
whether dsp2 or sp3} the central metal atom or ion of a 4-coordinated
complex ion undergoes depends on the number of unpaired or paired
electrons present in the complex ion.

Dr. Trupti Darji (V.P. and R.P.T.P. Science College) 7

 (1) Square Planar geometry (dsp2)
[Ni(CN)4]2- Tetracyanonickelate(II) :
j on
When [NI(CN)4]2-ion is square planar geometry, Ni2+ ion should be
dsp2 hybridised. In this hybridisation, due to the energy made available
by the approach of four CN- ions (ligands), the two unpaired 3d-electrons
are paired up, thereby, making one of the 3d orbitals empty. This empty
3d orbital (which is 3dx2-y2 orbital) is used in dsp2 hybridisation. This
hybridisation makes all the electrons paired (n = 0) and hence is
diamagnetic, as shown in Figure.

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Dr. Trupti Darji (V.P. and R.P.T.P. Science College) 8

 (2) Tetrahedral geometry (sp3)
A. [Ni(CO)4] molecule (Tetracarbonylnickel) :

In this complex compound Ni is in zero oxidation state and has its

valence-shell configuration as 3d84s2. This compound has tetrahedral
geometry which arises due to sp3hybridisation of Ni atom.
The magnetic studies of [Ni(CO)4] have indicated that this
molecule is diamagnetic (n = 0), showing that the two 4s electrons are
forced to pair up with 3d orbitals. This results in sp3 hybridisation and the
[Ni(CO)4] molecule has a tetrahedral structure in the figure.
8
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Dr. Trupti Darji (V.P. and R.P.T.P. Science College) 9

 B. [NICl4]2- ion (Tetrachloronickelate(II)g) o: ons

This complex ion has Ni2+ ion whose valence-shell configuration is

3d84s0. Magnetic measurements reveal that the given ion is
paramagnetic and has two unpaired electrons (n = 2). This is possible
only when this ion is formed by sp3 hybridisation and has tetrahedral
geometry in the figure.

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F
Limitations of Valence bond theory :

(1) VBT cannot account for the relative stabilities of different shapes and
different coordination numbers in metal complexes, e.g., it cannot
explain satisfactorily as to why Co(+2) (d8 system) forms both octahedral
and tetrahedral complexes while Ni(+2) (d7 system) rarely forms
tetrahedral complexes.

(2) VBT cannot explain as to why Cu(+2) forms only one distorted
octahedral complex even when all the six ligands are identical.

(3) This theory cannot account for the relative rates of reactions of
analogous metal complexes. e.g. [Mn(phen)3]2+ dissociates
instantaneously in acidic aqueous solution while
[Fe(phen)3]2+dissociates at a slow rate.

Dr. Trupti Darji (V.P. and R.P.T.P. Science College) 10

(4) The classification of metal complexes on the basis of their magnetic
behaviour into covalent (inner-orbital) and ionic (outer-orbital) complexes
is not satisfactory and is often misleading.

(5) VBT fails to explain the finer details of magnetic properties

including the magnitude of the orbital contribution to the magnetic
moments, i.e. although both tetrahedral (sp3 hybridisation) and outer-
orbital octahedral (sp2d2 hybridisation) complexes of Co(+2) (d7 system)
have three unpaired electrons and are, therefore, expected to haveµ
value equal to
3.87 B.M.; the tetrahedral complexes generally haveµ value in the range
of 4.4 - 4.8 B.M., while the octahedral complexes have still higher value
ofµ in the range of 4.7 - 5.2 B.M. The increase in the value ofµ is due to
the orbital contribution. Similar is the case with tetrahedral and
octahedral complexes of Ni(+2) (d8 system). VBT cannot explain the
increase in the value ofµ.

(6) VBT cannot interpret the spectra (colour) of the complexes.

(7) This theory does not predict or explain the magnetic behaviours of
complexes. This theory only predicts the number of unpaired electrons.
Its prediction even for the number of unpaired electrons and their
correlation with stereochemistry is misleading. VBT cannot explain the
temperature dependent paramagnetism of the complexes.

(8) VBT cannot give any explanation for the order of reactivities of
inner-orbital inert complexes of d3, d4, d5 and d6 ions of the observed
differences in the energies of activation in a series of similar complexes.

(9) The magnetic moment values of the complexes of certain ions (e.g.,
Co2+, Ni2+ etc.) are much higher than those expected by spin-only
formula. VBT can not explain the enhanced values of magnetic
moments.

Dr. Trupti Darji (V.P. and R.P.T.P. Science College) 11