Valence Bond Theory

(VBT)
Nature of metal-ligand bonding in complex compounds
• 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, modem
theories have been proposed to explain the nature of metal-ligand
bonding in complexes.
• These theories can also explain the:
– Colour
– Geometry
– Magnetic properties
of the complex compounds.
• These modem theories are:
– Valence Bond Theory, VBT (due to L. Pauling and J L. Slater,
1935)
– Crystal Field Theory, CFT (due to H. Brethe, 1929 and Van Vleck,
1932)
– Ligand Field Theory, LFT or Molecular Orbital Theory, MOT (due
to I Van Vleck, 1935).
• Here we shall discuss only valence bond theory and crystal field 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
• This theory is based on the following assumptions:
1. The central metal atom or ion (as the case may be) makes available a
number of empty s, p and d atomic orbitals equal to its coordination
number.
• These vacant orbitals hybridise together to form hybrid orbitals
which are the same in number as the atomic orbitals hybridising
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 metals) complexes and the geometry of the complexes are
given in following table.
2. The ligands have at least one σ-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) σ-orbitals of the ligands to
form ligand → metal σ-bond (represented as
• This bond which is generally known as coordinate bond is a special
type of covalent bond and shows the characteristics of both the
overlapping orbitals.
• However, it also possesses a considerable amount of polarity
because of the mode of its formation.
4. The non-bonding electrons of the metal atom or ion are then
rearranged in the metal orbitals (viz. pure d, s or p orbitals as the
case may be) which do not participate in forming the hybrid orbitals.
• The rearrangement of non-bonding electrons takes place according
to Hund's rule.
Geometry of 6-coordinated complex ions
• Examples of 6-coordinated complex ions formed by some transition
metals are given in following table.
• In all these complex ions the coordination number of the central
metal atom or ion is six and hence these complex ions have
octahedral geometry.
• This octahedral geometry arises due to d2sp3 or sp3d2 hybridisation
of the central metal atom or ion.
• What type of hybridisation (i.e., whether sp3d2 or d2sp3) will occur
depends on the number of unpaired or paired electrons present in
the complex ion.
• d2sp3 or sp3d2 hybridisation is also called octahedral hybridization.
• 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.
• Now let us see how d2sp3 / sp3d2 hybridisation takes place in
octahedral complexes.
d2sp3 Hybridization 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. t2g or dε and eg
or dr.
• t2g set consists of dxy, dyz, and dzx orbitals while eg set has dz2 and
dx2-y2 orbitals.
• In the formation of six d2sp3 hybrid orbitals, two (n - 1) d-orbitals
of eg set [i.e., (n - 1) dz2 and (n - 1) dx2-y2 orbitals], 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 d2sp3 hybridisation are from
penultimate shell [i.e. (n - 1)th shell] while s and three p-orbitals are from
ultimate shell (i.e., 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 (eg set of orbitals) while s- and p-orbitals are 4s
and 4p orbitals.
• Thus d2sp3 hybridisation taking place in such complexes can be
represented as 3dx2-y2 . 3dz2 . 4s . 4px . 4py . 4pz (d2sp3).
• Since two d-orbitals used in d2sp3 hybridisation belong to inner
shell [i.e., (n - 1)th shell], the octahedral complex compounds
resulted from d2sp3 hybridisation are called inner orbital octahedral
complexes.
• Since these complexes have comparatively lesser number of
unpaired electrons than the outer-orbital octahedral complexes (see
later on), these complexes are also called low spin or spin paired
octahedral complexes.
• It is due to the presence of strong ligands in inner-orbital octahedral
complexes of 3d transition series that the electrons present in 3dz2
and 3dx2-y2 orbitals (eg set) are forced to occupy 3dxy, 3dyz, and 3dxz
orbitals (t2g set) and thus 3d orbitals of eg set become vacant and
hence can be used in 3dx2-y2 . 3dz2. 4s. 4px . 4py . 4pz (d2sp3)
hybridisation.
• Now let us discuss the structure of some octahedral complex ions of
3d transition series elements which result from d2sp3 hybridisation.
1. Ferricyanide ion, [Fe(CN)6]3- [Also called hexacynoferrate
(III) ion]
• In this ion the coordination number of Fe is six and hence the
given complex ion is octahedral in shape.
• In this ion, Fe is present as Fe3+ ion whose valence-shell
configuration is 3d5 or t32g e2g (Fe = 3d64s24p0, Fe3+ = 3d5 =
t32g e2g) as shown in following figure.
• According to Hund's rule, each of the five electrons in 3d
orbitals is unpaired in free Fe3+ ion (uncomplexed ion) and
hence the number of unpaired electrons (n) is equal to 5.
• However, magnetic study of [Fe(CN)6]3- ion has shown that
this ion has one unpaired electron (n = 1) and hence is
paramagnetic.
• Thus, in the formation of this ion, two electrons of eg set of 3d
orbitals (i.e., 3dz2 and 3dx2-y2 orbitals) pair up with the three
electrons of t2g set of orbitals (i.e., 3dxy, 3dyz and 3dzx orbitals).
• This results in that eg set of orbitals becomes vacant and is
used in d2sp3 hybridisation.
• This also results in that the valence-shell configuration of Fe3+
ion gets changed from t32g e2g to t52g e0g and thus the number of
unpaired electrons in 3d orbital now becomes equal to 1.
• Now 3dx2-y2, 3dz2 (eg set), 4s and three 4p (4px, 4py and 4pz
orbitals combine together and give rise to the formation of six
3dz2 . 3dx2-y2 . 4s. 4px . 4py . 4pz hybrid orbitals (d2sp3
hybridisation).
• Each of these hybrid orbitals is vacant.
• Each of the six CN- ions (ligands) donates its lone pair of
electrons to d2sp3 hybrid orbitals and six coordinate
bonds are established.
• The above discussion shows that [Fe(CN)6]3- ion has one unpaired
electron and hence is paramagnetic.
• It is an inner orbital octahedral complex ion, since it is formed by
d2sp3 hybridisation.
2. Ferrocyanide ion, [Fe(CN)6]4- [Also called hexacyano ferrate (II)
ion]
• 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 t42g e2g 4s0 4p0 which shows that Fe2+
ion has 4 unpaired electrons.
• Magnetic studies 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 d2sp3 hybridisation (see following 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 following figure.
3. Pentacyano nitrosyl ferrate (II) ion, [Fe2+(CN)5(NO+)]2- (Also
called nitroprusside ion)
• Since the coordination number of Fe is six, the given ion has
octahedral geometry.
• Pauling (1931) and Sidgwick (1935) have suggested that NO is
present as NO+ ion (nitrosyl ion) which is a two-electron donor.
• NO+ ion is obtained when NO molecule (5 + 6 = 11 electrons)
loses its unpaired electron residing in its π*y molecular orbital
[Molecular orbital configuration of NO molecule is (σb2s)2 (σ*2s)2
(σbx)2 (πby)2 (πbz)2 (π*y)1. Thus molecular orbital configuration of
NO+ ion (5 + 6 - 1 = 10 electrons) is (σb2s)2 (σ*2s)2 (σbx)2 (πby)2
(πbz)2 (π*y)0.
• The presence of NO+ ion in the given complex ion indicates that
Fe is present as Fe2+ ion (Fe2+ = 3d64s0 = t42g e2g 4s0 having n =
0).
• Magnetic moment value of [Fe(CN)5(NO)]2- ion has shown that
the given ion has no unpaired electron (n = 0) and hence is
diamagnetic.
• In order to account for its diamagnetic character, it is assumed
that the two electrons of eg orbitals are forced to occupy the t2g
orbitals so that we have all the electrons in the paired state and
two 3d orbitals of eg set become vacant and hence available for
d2sp3 hybridisation.
• Thus the given ion results from d2sp3 hybridisation and hence is
inner-orbital octahedral complex ion (see following figure).
4. Cobaltic nitrite ion, [Co(NO2)6]3- [Also called hexanitro cobaltate
(III) ion]
• It is evident from the fact that since the coordination number of Co3+
ion is 6, the given complex ion has octahedral geometry.
• Magnetic studies have shown that the given complex ion has no
unpaired electrons and hence the ion is diamagnetic.
• It is due to diamagnetic character that all the six electrons of the
valence shell of Co3+ ion (Co3+ = 3d6 4s0 4p0 or t42g e2g 4s0 4p0) are
paired in t2g set of orbitals and eg set becomes vacant, i.e., the
configuration of Co3+ ion in the complex ion is t62g e0g 4s0 4p0.
• Thus eg orbitals become vacant and hence are used in d2sp3
hybridisation. It is due to strong character of NO-2 ions (ligands) that
the two electrons of eg set are forced to occupy t2g orbitals. (see
following figure).
5. Inner orbital octahedral complexes of Co(+2)
• Examples of such complexes are [Co(NO2)6]4- and [Co(CN)6]4-
Both these ions are paramagnetic corresponding to the presence
of one unpaired electron.
• The valence-shell electronic configuration of Co2+ ion in its free
state is 3d7 4s0 4p0 5s0 or t52g e2g 4s0 4p0 5s0 which shows that
this ion has 3 unpaired electrons.
• Pauling has suggested that, in order to have only one unpaired
electron, one electron of eg orbitals is forced to occupy t2g
orbitals and the other electron of eg set is promoted to the higher
energy vacant 5s orbital.
• Thus now the configuration of Co2+ ion becomes t62g e0g 4s0 4p0
5s1 in which the number of unpaired electrons is equal to one
and both 3d orbitals of eg set become empty and hence are
available for d2sp3 hybridisation.
• The formation of [CoL6]4- ion (L = NO-2 or CN-) by d2sp3
hybridisation has been shown in following figure.
• The presence of unpaired electron in 5s orbital is
supported by the fact that, since 5s orbital is of very high
energy, the single electron residing in it should be
unstable and hence should be easily lost.
• Experimentally it has been found to be true.
• When [CoL6]4- ion is acted upon by air or H2O2, the
unpaired electron is lost and [Co2+L6]4- ion is oxidised to
[Co3+L6]3- ion.

• Thus we find that Co(+2) low spin (inner orbital)

octahedral complexes are unstable (are labile) and hence
are easily oxidised to Co(+3) complexes by air or H2O2.
• Consequently such complexes should be prepared in an
inert atmosphere.
6. Hexachloroplatinate (IV) ion, [PtC16]2-
• Since the coordination number of Pt4+ ion is six, the given complex
ion is octahedral in shape.
• Valence-shell configuration of Pt4+ is 4f14 5d6 6s0 6p0 or 4f14 t42g e2g
6s0 6p0 which has 4 unpaired electrons (n = 4).
• Magnetic study of [PtC16]2- ion has shown that this ion has no
unpaired electron (n = 0) and hence is diamagnetic.
• Thus in the formation of this ion both electrons of eg orbitals (5dz2
and 5dx2-y2 orbitals) are forced to occupy t2g orbitals (5dxy, 5dyz and
5dzx orbitals) and thus the number of unpaired electrons becomes
equal to zero (n = 0) and also eg orbitals become available for d2sp3
hybridisation.
• Thus we find that [PtC16]2- ion results from d2sp3 hybridisation of
Pt4+ ion (see following figure).
• Examples of some inner-orbital octahedral complexes are given in
following table.
sp3d2 Hybridisation in outer octahedral complexes
• This type of hybridisation takes place in those octahedral complex
ions which contain weak ligands.
• Weak ligands are those which cannot force the electrons of dz2 and
dx2-y2 orbitals (eg set) of the inner shell to occupy dxy, dyz and dzx
orbitals (t2g set) of the same shell.
• Thus in this hybridisation, (n — 1) dz2 and (n — 1) dx2-y2 orbitals
are not available for hybridisation.
• In place of these orbitals, we use ndz2 and ndx2-y2 orbitals (These d-
orbitals belong to the outer shell) and hence sp3d2 hybridisation can
be represented as ns. npx. npy. npz. ndz2. ndx2-y2 .
• This hybridisation shows that all the six orbitals involved in
hybridisation belong to the higher energy level (outer shell).
• This discussion shows that in case of octahedral ion of 3d transition
series, d-orbitals used in hybridisation are 4dz2 and 4dx2-y2 orbitals.
• Since two d-orbitals are from the outer shell (i.e., nth shell), the
octahedral complexes resulted from sp3d2 hybridisation are called
outer orbital octahedral complexes.
• Since these complexes have comparatively greater number of
unpaired electrons than the inner orbital octahedral complexes,
these are also called high spin or spin free octahedral complexes.
• Now let us discuss the structure of some octahedral complex ions of
3d transition series elements which are formed by sp3d2
hybridisation.
1. Hexafluroferrate (III) ion, [FeF6]3-
• In this ion, the coordination number of Fe is six and hence the given
complex ion has octahedral geometry.
• Here iron is present as Fe3+ whose valence shell electronic
configuration is 3d54s04p0 or t32g e2g 4s0 4p0.
• Each of the five electrons is unpaired and hence n = 5.
• Magnetic properties of the given ion have also shown that the ion
has five unpaired electrons and hence is paramagentic
corresponding to the presence of five unpaired electrons.
• Thus two electrons residing in eg orbitals cannot be forced to
occupy t2g orbitals as we have done in case of [Fe(CN)6]3- ion,
otherwise the number of electrons would become equal to one.
• Thus we find that in case of the given ion, the two d-orbitals used in
hybridisation are 4dz2 and 4dx2- y2 and s and p orbitals are 4s and 4p.
• Thus the given ion results from (4s) (4p3) (4dz2) (4dx2-y2) hybridisation as
shown in following figure.
• This discussion shows that in the formation of [FeF6]3- ion the original
valence-shell configuration of Fe3+ ion is not disturbed.
2. Pentaquanitrosonium iron (I) ion, [Fe+(NO+)(H2O)5]2+
ion
• This ion is obtained when NO gas is passed through a
freshly-prepared aqueous solution of FeSO4.

• Since the coordination number of Fe atom is six, the given

ion has octahedral geometry.
• The magnetic moment of this ion has been found to be
equal to 3.89 B.M. which shows that the given ion has
three unpaired electrons, i.e., Fe is present as Fe+ ion (Fe+
= 3d6 4s1 or 3d7 4s0 or t52g e2g 4s0 having n = 3).
• In order to show +2 charges on the complex ion, NO is
assumed to be present as nitrosyl cation (NO+) which is a
two-electron donor.
• In order to show the presence of three unpaired electrons
in the given ion, t52g e2g configuration of Fe+ ion is not
disturbed.
• This means that d2sp3 hybridisation scheme cannot be used
to account for the presence of three unpaired electrons
(d2sp3 hybridisation gives one unpaired electron which
would not be present in t2g set of orbitals but in some other
orbital).
• We assume that the given ion results from sp3d2
hybridisation and hence the given ion is an outer-orbital
octahedral ion (see following figure).
3. Outer-orbital octahedral complexes of Ni(+2)
• Octahedral complexes of Ni2+ ion are outer-orbital octahedral
complexes (sp3d2 hybridisation).
• The formation of inner-orbital octahedral complexes of Ni2+ ion
(Ni2+ = 3d8 = t62g e2g ) is not possible, since the two unpaired
electrons present in eg set of orbitals cannot be sent to t2g orbitals
which are already completely filled.
• Thus eg orbitals cannot be made empty for d2sp3 hybridisation.
• Outer orbital complexes of Ni2+ ion are paramagnetic
corresponding to the presence of two unpaired electrons present in
eg orbitals.
• As an example let us see how sp3d2 hybridisation takes place in
[Ni(NH3)6]2+ ion (See following figure).
• Examples of some outer-octahedral complexes are given in
following table.
 Geometry of 4-coordinated complex ions
• Examples of 4-coordinated complex ions formed by some
transition metals are given in following table.
• 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
Important
↓

dsp2 or sp3 hybridised.

• What type of hybridisation (i.e., whether dsp2 or sp3) the central
metal atom or ion of a 4-coordinated complex ion undergoes
Important

depends on the number of unpaired or paired electrons

↓

present in the complex ion.

Square planar complex ions
• Here we shall consider the following complex ions.
1. [Ni(CN)4]2- ion
• In this complex ion, since the coordination number of Ni2+ ion is
4, the given complex ion may be square planar or tetrahedral in
shape.
• In order to decide whether the given complex ion is
square planar or tetrahedral, we take the help of magnetic
property of the complex ion.
• Experimentally it has been shown that [Ni(CN)4]2- ion has
no unpaired electron (n = 0) and hence is diamagnetic.
• Two cases arise:
(a) When [Ni(CN)4]2- ion has tetrahedral geometry
• In this case Ni2+ ion is sp3 hybridised as shown in
following figure.
• sp3 hybridisation scheme given in following figure shows
that [Ni(CN)4]2- ion has two unpaired electrons (n = 2).
(b) When [Ni(CN)4]2- ion has square planar geometry
• For getting this 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)
as shown in following figure.
Conclusion
• We have said above that experiments have shown that
[Ni(CN)4]2- ion has no unpaired electron (n = 0) and
hence is diamagnetic.
• This magnetic property confirms the fact that [Ni(CN)4]2-
ion has square planar geometry with n = 0 and not
tetrahedral geometry with n = 2.
2. [Cu(NH3)4]2+ ion (Oxidation of Cu2+ to Cu3+ does not occur)
• Since the coordination number of Cu2+ ion is 4, the given
complex ion has either square planar or tetrahedral
geometry.
• Square planar geometry arises due to dsp2 hybridisation of
Cu2+ ion as shown in following figure while tetrahedral
geometry is due to sp3 hybridisation of Cu2+ ion as shown
in following figure.
Square planar geometry
↓
dsp2
Tetrahedral geometry
↓
sp3
• As is evident from above figures that in both the geometries,
[Cu(NH3)4]2+ ion has one unpaired electron (n = 1).
• In square planar geometry, the unpaired electron resides in 4p
orbital while in tetrahedral geometry this electron is present in
3d orbital.
• The above discussion shows that the magnetic property of
[Cu(NH3)4]2+ ion cannot be helpful in deciding as to what is
the exact geometry of [Cu(NH3)4]2+ ion.
• However, physical measurements have indicated that the
tetrahedral geometry for [Cu(NH3)4]2+ ion is not possible.
• Now if the square planar geometry for [Cu(NH3)4]2+ ion is
supposed to be correct, the unpaired electron present in the
higher energy 4p orbital (dsp2 hybridisation) should be
expected to be easily lost, i.e., [Cu(NH3)4]2+ ion (Cu = +2)
should be easily oxidised to [Cu(NH3)4]3+ ion (Cu = +3) by
losing the unpaired electron residing in 4p orbital.
 (Does not possible)
• However, experiments have shown that the oxidation of
[Cu(NH3)4]2+ to [Cu(NH3)4]3+ as shown above does not occur.
• Then how to explain the geometry of [Cu(NH3)4]2+ ion.
Huggin's suggestion
• Huggin has suggested that [Cu(NH3)4]2+ ion has square
planar geometry and Cu2+ ion is sp2d [(4s)(4p)2(4d)]
hybridised as shown in following figure.
• The unpaired electron resides in 3d orbital.

Conclusion
• [Cu(NH3)4]2+ ion → square planar geometry
• Cu2+ ion → sp2d [(4s)(4p)2(4d)] hybridised
• Unpaired electron → 3d orbital
Square planar geometry
↓
4(sp2d)
3. [Ni(dmg)2]0 molecule
• In this complex compound, Ni is present as Ni2+ ion (Ni2+
= 3d8 4s0).
• dmg is a negatively-charged ion which acts as a bidentate
ligand.
• Magnetic measurements have shown that [Ni(dmg)2]0 has
no unpaired electrons (n = 0) and has square planar
geometry which arises because of dsp2 hybridisation of
Ni2+ ion.
• For getting dsp2 hybridisation, one 3d orbital should be
vacant.
• In order to make 3d orbital vacant, two unpaired electrons
present in 3d orbitals are forced to get paired (see
following figure).
Tetrahedral complex ions
• Here we shall discuss the structure of the following
complex compounds which have tetrahedral geometry.
1. Ni(CO)4 molecule (Ni → zero oxidation state)
• 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 sp3 hybridisation 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 Ni(CO)4 molecule
has tetrahedral structure (see following figure).
2. [NiCl4]2- ion (Ni → +2 oxidation state)
• This complex ion has Ni2+ ion whose valence-shell configuration as
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 (see following figure).
To find out the number of unpaired electrons in a given complex
ion
• The number of unpaired electrons (n) present in a given complex
ion depends on the geometry of the complex ion and the type of
hybridisation undergone by the central metal atom or ion.
• This is evident from following table in which we have shown a
relation between the number of unpaired electrons and geometries
of the complex ions.
Limitations of VBT
1. VBT cannot account for the relative stabilities for different
shapes and different coordination numbers in metal
complexes, e.g., it cannot explain satisfactorily as to why
Co(+2) (d7 system) forms both octahedral and tetrahedral
complexes while Ni(+2) (d8 system) rarely forms tetrahedral
complexes.
• Similarly, Fe(+3) (d5 system) forms both tetrahedral and
octahedral complexes while Cr(+3) (d3 system) gives only
octahedral complexes.
2. VBT cannot explain as to why Cu(+2) forms only one
distorted octahedral complexes 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
instantaneusly in acidic aqueous solution while [Fe(phen)3]2+
dissociates at a slow rate.
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, e.g., many of the so-called ionic complexes like
[Fe3+(acac)3]0 have properties like high volatility, high solubility
in organic solvents etc. which are characteristics of covalent
compounds.
• Also it is known that the aquo ion, [Cr(H2O)6]3+ (pKa = 3.8 at
25°C) is a much weaker acid than [Fe(H2O)6]3+ (pKa = 2.2) and
[Co(H2O)6]3+ (pKa = 0.7) ions, despite the fact that only
[Fe(H2O)6]3+ is of outer-orbital type with ionic bonding while the
other two aquo ions are of outer-orbital type with covalent
bonding.
• Both [Fe(H2O)6]3+ and [Co(H2O)6]3+ ions exchange H2O18 in
solvent instantaneously while [Cr(H2O)6]3+ ion exchanges H2O18
very slowly.
• The acidity of an aquo metal ion is expected to increase with the
increase of covalent character of the metal-oxygen bond.
• But neither the sequence of acidities nor the exchange rates of the
above mentioned three aquo metal ions are in the order expected
from their classification into ionic and covalent types on the basis
of Pauling's VBT.
5. VBT fails to explain the finer details of magnetic properties
including the magnitude of the orbital contribution to the magnetic
moments, e.g. although both tetrahedral (sp3 hybridisation) and
outer-orbital octahedral (sp3d2 hybridisation) complexes of Co(+2)
(d7 system) have three unpaired electrons and are, therefore,
expected to have μ value equal to 3.87 B.M.; the tetrahedral
complexes generally have μ value in the range of 4.4 – 4.8 B.M,
while the octahedral complexes have still higher value of μ in the
range of 4.7 – 5.2 B.M.
• The increase in the value of μ 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 of μ.
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.
• For example it was assumed for long that all square planar
complexes of Ni(+2) (d8 system) formed by dsp2 hybridisation were
diamagnetic (n = 0), while all tetrahedral complexes of Ni(+2)
formed by sp3 hybridisation were paramagnetic due to the presence
of two unpaired electrons (n = 2).
• X-ray study of 4-coordinate Ni(+2) complexes has shown that one
and the same complex can be obtained in both a paramagnetic form
(having blue colour) and a diamagnetic form (having yellow
colour).
• VBT has no explanation for it.
• VBT cannot explain the temperature dependent paramagnetism of
the complexes.
8. VBT cannot give any explanation for the order of reactivities of the
inner-orbital inert complexes of d3, d4, d5 and d6 ions and 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 moment.
The End