UNIT- 2 METAL LIGAND BONDING IN TRANSITION

METAL COMPLEXES

CONTENTS:
2.1 Objectives
2.2 Introduction
2.3 Limitations of valence bond theory
2.4 An elementary idea of crystal field theory
2.5 Factors effecting the crystal field parameter
2.6 Applications of the CFT
2.7 Limitations of CFT
2.8 Ligand field theory and molecular orbital theory
2.9 Summary
2.10 Terminal questions

2.1 OBJECTIVES

This unit will help you to answer the following questions:

• What are the limitations of valence bond theory?
• What is the relative strength of a ligand?
• How can we compare the stability of complexes?
• What are the regions for colours associated with transition metal complexes?
• What are the basic premises of crystal field theory (CFT)?
• How molecular geometries associated with various d-orbital splitting patterns?
• How spectral and magnetic properties of transition metal complexes can be explained
in terms of CFT concepts?

2.2 INTRODUCTION

Bonding in coordination chemistry has been described by many theories. In order to

explain various properties exhibited by complexes, these theories were modified time to time.
INORGANIC CHEMISTRY- III BSCCH-301

The theory of Effective Atomic Number (EAN) rule was first used but found to be inadequate
as behaviour of many complexes could not be explained by this method. The EAN rule states
that stable compound should have electronic configuration of its nearest noble gas. There are
many exceptions to this rule because it limits the coordination number possible for each
metal. Octahedral complexes of many compounds show exception to this theory. However,
the theory is sufficient to explain the bonding in metal complexes with metal in zero
oxidation state.
Examples are [Ni(CO)4] and [Cr(CO)6] where the central metal has zero oxidation
number and accommodates ligands sufficient enough to have the electronic configuration of
their nearest noble gas. The theory cannot explain the reason for variation in coordination
number, hence the need for another theory. Valence bond theory (VBT) is introduced to
explain the reason for the variation in coordination number based on the number of
hybridized orbitals of the metal used in bonding. It cannot explain fully the concept of colour
and magnetic properties of complexes. Crystal Field Theory (CFT) is used to provide
explanation for the spectra and magnetic properties of complexes.

2.3 LIMITATIONS OF VALENCE BOND THEORY

Valence Bond Theory (VBT) is a hybridization based theory proposed by the Pauling.
According to them, metal- ligand bonding in a complex compound is of 100% covalent
nature but there are certain limitations related to this theory which can be given as:
1. VBT cannot give the idea about the relative stabilities for different shapes and
different coordination numbers in transition metal complexes, e.g. it cannot explain
satisfactorily as to why Co+2 (d7 configuration ) forms both tetrahedral and octahedral
complexes while Ni+2 (d8 configuration) rarely form tetrahedral complexes.
2. VBT cannot explain why Cu+2 forms only distorted octahedral complexes even when
all the six ligands are identical.
3. VBT cannot give the idea about the colour of the complexes.
4. VBT was failed to explain the strength of the ligands i.e. it cannot explain that which
of the ligands will be called as stronger or weaker ligand.
5. According to the VBT magnetic moment of the complexes can determined by the
following equation:
µs = B.M.
 But the actual value of magnetic moment is found to be slightly greater than as
calculated by the above equation, which cannot be explained by VBT. In other word,
we can say that VBT cannot give the idea about the orbital contribution in the
magnetic moment of complexes.
6. This theory does not predict the magnetic behaviours of complexes. This theory only
predicts the number of unpaired electrons and their correlation with stereochemistry is
misleading. For example it was assumed that all the square planar complexes of Ni+2
(d8 configuration) formed by dsp2 hybridization, were diamagnetic in nature, while
all tetrahedral complexes of Ni+2 formed by sp3 hybridization were paramagnetic due
to the presence of two unpaired electrons. By the X- ray analysis, it was observed that
Ni+2 complexes have shown that one and the same complex can be obtained in both,
paramagnetic form and diamagnetic form. VBT has no explanation for it.
7. According to VBT, inner orbital octahedral complexes with d2sp3 hybridization are
covalent in nature and outer orbital octahedral complexes with sp3d2 hybridization are
ionic in nature but there are certain complexes which have covalent character
according to VBT but exhibit ionic property, which cannot be explained by VBT.
8. VBT cannot give any explanation for the order of reactivates of the inner orbital inert
complexes of d3, d4, d5 & d6 ions and of the observed differences in the energies of
activation in a series of similar complexes.
9. VBT was failed to explain the kinetics of the complexes.

2.4 AN ELEMENTARY IDEA OF CRYSTAL FIELD THEORY

In view of the above weaknesses, an alternative bonding model was applied to

transition metal complexes. This is known as crystal field theory (CFT). Brethe and Van
Vlick have been proposed a theory to explain the bonding in the ionic crystals, which is
called as Crystal Field Theory (CFT). Initially this theory was propound for the ionic crystals
but in 1952 Vage has been proposed this theory for the metal-ligand bonding in the complex
compounds, which is known as CFT of the Coordination Chemistry.
Some of the postulates related to the CFT can be given as:
1. According to the CFT, central metal ion (CMI) of the complexes being surrounded by
a number of ligands.
 2. According to this theory, ligands can be of the two types which are given below:
a. Negative ligandse.
b. Neutral ligands also known as point dipole.
3. According to CFT, there does not occur any type of the overlapping between the
orbitals of the ligand and CMI i.e. metal ligand bonding having zero % covalenay.
4. According to CFT, always there occur an electro static interaction between the +ve
charge nucleus of the CMI and –ve charge of the ligand i.e. metal- ligand bonding
having 100% ionic character. Complexes are thus presumed to be formed when CMI
electrically attract ligand which may be either anions or dipolar molecules.
If the complex contas neutral ligand, then the –ve pole of neutral ligand (point dipole)
will be oriented towards the CMI.

2.4.1 CFT for the octahedral complexes

CFT of octahedral complexes can be defined in the following steps:-

Step I- Shape of 5- d orbital’s of CMI
Five d- orbitals of the CMI can be divided into two different set of orbital’s as given
below:
a. t2g set (Non-axial set of d-orbitals)
Three orbitals namely dxy dyz and dzx orbitals are known as t2g set of d orbitals. All
these orbital being present between the axis due to which they are also known as Non-
axial set of d- orbitals.
b. eg set (Axial set of d- orbitals):
Two orbitals namely dx2- y2 and dz2 are combindly known as eg set of d orbitals. Both
these orbitals being present over the axis due to which they are also known as axial set
of d-orbitals (Figure 2.1).
 x y x
+ - + - + -
y z z
- + +
- - +

t 2 g orbitals (non axial)

x
z
+
+

- - y - -

+ +

eg orbitals (axial)

Figure 2.1: Different types of d-orbitals

Step II- Orientation of 6 ligands around the CMI in the octahedral complexes
In the octahedral complexes, all the six ligands being oriented toward the CMI from
the six opposite corners of the three cartition axis, which can be represented as:
L
L
L

M+n

L
L
L

or
L
L

L
M

L L

Step III- Crystal field splitting of the 5 d orbitals of CMI

 When the CMI being present in the isolated form, then all the five d orbitals of the
CMI have same energy and they are combindly known as degenerates of 5-d orbitals but if
the ligand comes in the environment of CMI, the hypothetical energy of all the 5 d orbitals
slightly increased due to the repulsion between the –ve charge of the ligand and 5 d orbitals.
Finally, when the 6 ligands comes in the octahedral environment around the CMI to construct
the octahedral complex, then 5 d orbitals of the CMI split into the lower energy t2g set and
higher energy eg set of orbitals, which is called as crystal field splitting in the octahedral
complexes. The energy difference between the spillited set of orbitals is known as crystal
field splitting energy difference (∆o) (Figure 2.2).

Figure 2.2: Crystal field splitting of d orbitals in octahedral complex

Step IV-Distribution of dn configuration of the CMI in the splitted set of d-

orbitals
To define the distribution of dn configuration of CMI in the splitted set of d-orbitals,
at first we have to define the strength of ligand i.e. spectro chemical series.
Spectrochemical Series: According to the concept of CFT, those ligands which have the
more splitting power, are known as stronger ligands while on the other hand, those ligands
which have the less spitting power, are known as weak ligands. After arranging the various
ligands in order of their uncrossing or decreasing splitting power, the arrangement which is
obtained is known as spectro chemical series.
Arrangement of certain ligands in order of their increasing splitting power according
to spectrochemical series can be given as:
I− < Br− < S−2 < SCN− < Cl− < NO2− < F− < OH− < H2O < NCS− < py < bipy < CN− < CO
The ligands interact weakly: - weak field ligands e.g. I−, Br−, S−2, SCN−, Cl−
The ligands interact strongly: - strong field ligands e.g. NO,CN− ,CO
Similarly, if metal ions are different with same ligand, ∆o will be different. Metals
with more positive charge and from 2nd and 3rd transition series interact more (higher
splitting).
Now distribution of dn configuration of the CMI can be given under the two
conditions:-
(a) If o> P i.e. under the strong field octahedral condition
If the octahedral complex contains stronger ligand, than the value of o being

greater than the mean pairing energy (p). Under such condition, distitution of the dn
configuration of CMI in the splitted set of d-orbitals can be given as shown in Figure
2.3.
eg eg

(t2g1,eg0 )
d1 (t2g6,eg1 )
d7

t2g t2g

eg eg

(t2g2,eg0 ) (t2g6,eg2 )
d2 d8

t2g t2g

eg eg

(t2g3,eg0 ) (t2g6,eg3 )
d3 d9

t2g t2g

eg eg

(t2g4,eg0 ) (t2g6,eg4 )
d4 d10

t2g t2g
eg

(t2g5,eg0 )
d5

t2g

eg

(t2g6,eg0 )
d6

t2g

Figure 2.3: Splitting of dn configuration under the influence of strong field ligands
(b) If o <P i.e. under the weak field octahedral condition
If the octahedral complex contains weak ligands, then the value of o being
less than mean pairing energy (P). Under such condition, distribution of the dn
configuration of the CMI splits into set of d orbitals that can be given as shown in
Figure 2.4.
eg eg

(t2g1,eg0 )
d1 (t2g5,eg2 )
d7

t2g t2g

eg eg

(t2g2,eg0 ) (t2g6,eg2 )
d2 d8

t2g t2g

eg eg

(t2g3,eg0 ) (t2g6,eg3 )
d3 d9

t2g t2g

eg eg

(t2g3,eg1 ) (t2g6,eg4 )
d4 d10

t2g t2g
eg

(t2g3,eg2 )
d5

t2g

eg

(t2g4,eg2 )
d6

t2g

Figure 2.4: Splitting of dn configuration under the influence of weak field ligands in octahedral
complex
 Step V: Crystal field stabilization energy in the octahedral complexes
Crystal field splitting of the dn configuration in the octahedral complexes can be given as:

eg

0.6 ∆o
d n ∆o
-0.4 ∆o
t2g
Suppose total number of electrons (e–) in t2g set = p (1 to 6)
Total no of e– in eg set = q (1to 4)
Than decrease in energy of dn configuration by entrance of 1 e- in t2g set = -0.4 ∆o
So, decrease in energy of dn configuration by entrance of p e- in t2g set = (-4. o) p
Increase in energy of d dn configuration by entrance of 1e- in eg set = 0.6 ∆o
So, increase in energy of dn configuration by enterance of q e- in eg set = (0.6 o) q
Thus, total energy change of dn configuration = (-0.4 0) p + (0.6 0) q
= (-0.4p + 6q) 0

This total amount of the energy change for the dn configuration is known as crystal
field stabilization energy (CFSE) for the dn configuration of CMI in the octahedral complexe.
Thus,
CFSE= (-0.4p +0. 6q) 0

If the value of mean pairing energy being P and number of pairs of electrons in the t2g
or eg orbitals being n, then nP amount of energy will also increases the energy of dn
configuration.
Thus, the net energy will be

CFSE= (-0.4 p +0.6q) o + nP

2.4.2. CFT for the tetrahedral complexes

CFT for tetrahedral complexes can be explained under the five different steps, which
are given below:
Step I Shape of 5- d orbitals: All the 5-d orbitals of the CMI can be devided into 2
different sets of orbitals, which are given below (Figure 2.5).
 (a) ‘e’- set: dx2 – y2 and dz2 orbital are combindly known as ‘e’ set of axed set orbitals.
(b) t2 set: dxy , dyz & dzx orbitals are cmbindly known as ‘t2’ – set or non axial set of
orbitals.
x
z
+
+

- - y - -

+ +

e orbitals (axial)

x y x
+ - + - + -
y z z
- + + +
- -

t2 orbitals (non axial)

Figure 2.5: Two Set of d orbitals in tetrahedral complex

Step II- Orientation of 4 ligands around the CMI in the tetrahedral complexes
In the tetrahedral complexe, all the 4 ligands being oriented towards the CMI from the
non axial position that can be represented as:

M+n

L
INORGANIC CHEMISTRY- III BSCCH-301

Step III- Crystal filed splitting of the 5 d orbitals of CMI in tetrahedral

complexes
When the CMI being present in the isolated form, then all the 5 d orbitals of the CMI
have same energy and they are combindly known as degenerate set of 5 d orbitals, but when
the 4 ligands comes in the environment of CMI, then there occur the partial hypothetical
repulsion between the –ve charge of the ligands and all the 5 d orbitals due to which energy
of all the 5-d orbitals of CMI is slightly increased. Finally due to the tetrahedral environment
from the non axial position, there occur the splitting of all the 5 d orbitals of CMI into lower
energy e set and higher energy t2 set and this is known as crystal field splitting in the
tetrahedral complexes. The energy difference between the splitted set of d- orbitals is known
as crystal field splitting energy difference of tetrahedral complex (∆t) (Figure 2.6).

Figure 2.6: Crystal field splitting in tetrahedral complexes

Step IV- Distribution of dn configuration of CMI in the tetrahedral complexes

(Figure 2.7)
INORGANIC CHEMISTRY- III BSCCH-301

t2 t2

d 1
e1t20 e t233
d6

e e

t2 t2
2 0
d2 e t2 d7 e4t23

e e

t2 t2

d3 e2t21 d8 e4t24

e e

t2 t2

d4 e 2t22 d9 e4t25

e e

t2 t2

d5 e2t23 d 10 e t26
4

e e

Figure 2.7: Splitting of dn configuration under the influence of weak field ligands in tetrahedral
complex

Step V- Crystal field stabilization energy in the tetrahedral complexes

Crystal field splitting diagram for the dn configuration of CMI in the tetrahedral
complexes can be represented as:

t2-set

0.4 ∆ t
6
d

-0.6 ∆ t
e- set

Suppose no. of e in e set = q (1to 4)

No. of e- in t2 set = p (1to 6)
Decrease in the energy of dn configuration due to the entrance of one e- in e set = -0.6 ∆t
Decrease in energy of dn configuration due to the entrance of qe- in e set = -0.6 ∆t x q
Increase in energy of dn configuration due to entrance of one e- in t2 set = 0.4∆t
So, increase in energy of dn configuration due to entrance of p e- in t2 set =0.4 ∆t x p
Net energy change of dn configuration = (-0.6 ∆t x q + 0.4 ∆t x p)
= (-0.6 x q + 0.4 x p) ∆t

This net amount of the energy change for the dn configuration is known as CFSE of the
tetrahedral complexes.
i.e. CFSE= (-0.6q + 0.4P) ∆t

Suppose the value of mean pairing energy is denoted by the symbol P and total
number of the pair in the splitted set of d orbitals denoted by the symbol n, then the nP
amount of energy will also be involved in the CFSE formula.
Thus
CFSE= (-.6q + .4P) ∆t + nP

2.4.3 CFT for the square planar complexes

CFT of the square planar complexes is arises from the CFT of octahedral complexes.
The crystal field splitting diagram for the square planer complexes originated from the
splitting diagram of octahedral complexes in the two steps which can be represented as:
If the two trans ligands in an octahedral ML6 complex (consider those along the z-
axis) are moved either towards or away from the metal ion, the resulting structure is said to
be tetragonally distorted. Ordinarily such distortions are not favored since they result in a net
loss of bonding energy. In certain situations, however, such a distortion is favored because of
a Jahn-Teller effect. A complex of general formula trans-Ma2b4 also will have tetragonal
symmetry. For now, we will consider the limiting case of tetragonal elongation, a square
planar ML4 complex, for the purpose of deriving its d-orbital splitting pattern. The crystal
field diagram for the tetragonally distorted complex and the square-planar complexes is
shown below. Removal of ligands from z-direction completely leads to the square-planar
geometry (Figure 2.8). This geometry is favoured by metal ions having a d8 configuration in
INORGANIC CHEMISTRY- III BSCCH-301

the presence of a strong field. This combination gives low-spin complexes where the first
four orbitals are occupied and the high-energy dx2-y2 orbital is unoccupied.

Lb Lb
Lb Lb
Lb La Lb
Slight removal of the La ligand +n
Slight removal of the La ligand M+n M
M
+n

Lb Lb Lb Lb
Lb Lb La
La Squar planner complex
M-La # M-Lb
M-La = M-Lb
Pure octahedral complex
(Distorted octahedral)
Figure 2.8. Formation of square planare complex from octahedral complex
Crystal Field splitting for square planar complex
Square planar complexes are similar to the octahedral complexes. The difference is
that square planar complexes have two ligands missing in the z axis. There is a very large
energy gap between the dx2-y2 orbital and the lower four orbitals. Square planar complexes are
favored by metal ions with d8 electron configurations. Since this configuration favours low-
spin complexes in which the four lower-energy orbitals are filled and the high energy dx2-y2
orbital is empty. The crystal field splitting diagrame of square planar complex is given in
Figure 2.9.

d x 2 -y 2

sp 3

d x 2 -y 2
d xy
d x 2 -y 2 d z 2
d z2
n
d sp 2 sp
d xy

d xy d yz d zx d z2
d yz d zx
sp 1

d yz d zx

Figure 2.9. Crystal field splitting diagrame of square planar complex

2.5 FACTORS AFFECTING THE CRYSTAL FIELD PARAMETER

Some factors which can affect the value of ∆ (Crystal field splitting energy difference)
are given below:

2.5.1 Nature of ligands

With the increase in the strength of the ligands present in the complexes, the value for the
complexes is increases.
Explanation: With the increase in the strength of the ligand, the ability of the ligands to cause
the closer approach with the central metal atom (CMA) increases by which the repulsion
between the ligand and d orbitals as well as value also increases.
Examples:
a. [Fe(CN)6]-4 ion contains the stronger CN- ligands while (Fe(Cl)6]-4 ion contains the weak Cl-
ligands due to which the value for (Fe(CN)6]-4 ion is found to be more than (Fe(Cl)6]-4 ion.
b. [Co(F)6]-3 ion contas the stronger F- ligand while [Co(Cl)6]-3 ion contains the weak Cl- ligand
due to which the value for [Co(Cl)6]-3 ion is found to be less than [Co(F)6]-3 ion.

2.5.2 Nature of central metal atom (CMA)

a. Same CMA with different charge
If the complexes containing same CMA with the different charge, then the complex with the
higher +ve charge of the CMA will exhibit higher value.
Explanation: In the complexes containing different charge on the CMA, the complex with
the higher +ve charge of the CMA exhibit higher value because the CMA with higher +ve
charge can attract the ligand more closer toward itself by which the repulsion between the
ligand and d- orbitals of CMA as well as value is increases.
b. Different CMA with the different charge
If the complexes contain different charge, then the complex containing higher +ve charge
on the CMA exhibit higher value.
Explanation: If the complexes contain different CMA with the different charge, then the
complex containing higher +ve charge on CMA exhibit the higher value because the CMA
with the higher +ve charge can attract the ligand more closer toward itself due to which the
repulsion between the ligand and d- orbitals of CMA as well as value are increases.
Examples: a. [V(H2O)6]+2 complex ion contains lower +ve charge (+2) on the CMA while [Cr
(H2O)6]+3 ion contains higher + ve charge (+3) on the CMA due to which [Cr(H2O)6]+3 ion will
exhibit higher value.
b. [Fe(NH3)6]+3 ion contains higher + ve charge of the CMA (+3) while [Fe (NH3)6]+2 ion
contains lower + ve charge of the CMA (+2) due to which [Fe(NH3)6]+3 ion will exhibit
higher value.
c. Different CMA with same charge
If the complexes contain different CMA with the same charge, then that complex
containing lower dn configuration of CMA will exhibit higher value.
Explanation: This can be due to shielding effect.
Example: [Fe(H2O)6]+2 ion has 3d6 configuration of CMA while [Co(H2O)6]+2 ion contains the
3d7 configuration of CMA and both these complexes have same charge value, thus, the former
complex ion with lower dn configuration will exhibit high value.
d. Principal quantum no of dn configuration
With the increase in the Principal quantum number of dn configuration of CMA, the value
of is increases. In other word the value for the complexes of II-transition series elements
being 30% greater than the value for the complexes of I-transition series elements and the
value for the complexes of III- transition series element being greater than the II-transition series
elements.
Example: [Fe(CN)6]-4 ion exhibits lower value than the [Ru(CN)6]-4 ion because Ru have
higher Principal quantum number of dn configuration in comparison to Fe.

2.6 APPLICATIONS OF THE CFT

 The following properties of transition metal complexes can be explained on the basis of
CFT.
2.6.1. According the CFT, if the splitted set of d-orbitals of the CMI present in the complexes
contains the unpaired e- than the complex will be called as paramagnetic in napture while if the
splitted set of d-orbitales of the CMI does not contain the unpaid e-, then the complex will be
called as diamagnetic in nature.
Example:
(I) [(Co(F)6]-3 ion
Configuration of Co = 3d7, 4s2
Oxidation state of Co = +3
Configure of Co+3 = 3d6
According to CFT

eg

3d6

t2g

The splitted set of d- orbitals contain 4 unpaired e- due to which the complex ion [Co(F)6]-3 ion
will be paramagnetic in nature according to CFT and its magnetic moment will be:
µ= B.M.

µ= = 4.9. B.M.

(II) [Co(NH3)6]+3 ion

Configuration of Co = 3d7 4S2
Oxidation State of Co = +3
Configuration of Co+3 = 3d6

eg

3d6

t2g
According to CFT The splitted set of d- orbitals do not contain the unpaired e- due to which the
complex ion [Co(NH3)6]+3 ion will be diamagnetic in nature.
2.6.2 Stability of the oxidation states

With the help of CFT we can compare the stability of the different oxidation states
exhibited by a particular transition metal element under the strong field and weak field condition
by using the CFSE concept.
Example: Co (III) is more stabilized than the Co (II) under strong filed condition while Co (II) is
more stabilized than the Co (III) under the weak filed condition which can be explained by the
CFSE concept of CFT.
Configuration of Co(III) under strong field condition = t2g6
CFSE =6 x -0.4 ∆o + 3P (pairing energy) = -2.4 ∆o + 3P
Configuration of Co(II) under strong field condition = t2g6eg1
CFSE = 6 x -0.4 ∆o + 1 x 0.6 ∆o + 3P (pairing energy) = -1.8 ∆o + 3P
Configuration of Co(III) under weak field condition = t2g4eg2
CFSE =4 x -0.4 ∆o + 2 x 0.6 ∆o + 1P (pairing energy) = -0.4 ∆o + 1P
Configuration of Co(II) under strong field condition = t2g5eg2
CFSE = 5 x -0.4 ∆o + 2 x 0.6 ∆o + 2P (pairing energy) = -0.8 ∆o + 2P
Higher the value for CFSE, higher will be the stability of complex.

2.6.3 Colour of the complexes

To define the colour of the complexes formed by the d- block complex, at first, white
light is passed from the solution of complex compound then,
(i.) If whole of the white light is transmitted by the sample, then the complex will be called as
white in colour.
(ii.) If whole of the white light is absorbed by the sample, then the complex is called as black in
colour.
(iii.) If some of the radiations of the white light are absorbed and some other radiations are
transmitted, in such condition, the complex can be coloured only if the absorbed radiations
belong to the visible range (4000Aº – 7000 Aº)
When the complex absorbed the radiation of visible range, then the actual colour of the
complex will depend on the wavelength of that particular radiation which is absorbed by the
complex compound:-
4000A0 4350A0 4800A0 4900A0 5000A0 5600A0 5800A0 5900A0 6050A0 7000A0
Yellow
Colour of absorption Voilet Blue Green Blue Green Yellow Orange
green Red
blue Green

Yellow Yellow Blow

Orange Red Purple Voilet Blue
Complementry colour Green Green Green

The mechanism which is responsible for the colour in the complexes can be defined by d-
d transition phenomena.
According to d-d transition phenomena, when the e- present in the lower energy splitted
set of d- orbitals of the CMI obsorbs the radiation of any particular wavelength, then there occur
the transition of e- to the higher energy splitted set of d- orbitals, which is known as d-d
transition phenomena, that can be represented as:-

eg

3dn d-d transition

t2g

Color of the absorption as well as complementary colour corresponding to the d-d transition
phenomena have already been discussed.Those complexes which containing the d10 or d0
configuration of CMI being colourless because such complexes cannot exhibit the d-d transition
phenomena.

Factor affecting the colour of the colour of the complexes

 Colour of the complexes can be affected by the two different factors, which are given
below:
(a) Nature of the ligands: With the change is the strength of the ligands present in the
complexes, the value of crystal field splitting energy difference ( ) between the splitting set
of d- orbitals is changed by which the wavelength radiation for d-d transition phenomena as
well as colour of the complex is changed.
(b) Nature of the CMI: With the change in the + ve oxidation state of CMI present in the
complex, the value of also changed by which the wavelength of radiation for d-d transition
phenomena as well as colour of the complex will be changed.

2.6.4 Determination of the spinel structure

Mg+2 Al2+3 O4 is called as mineral spinel and accordingly all the mixed oxides having the
general formula A+2 B2+3O4 are known as spinals in which both the A+2 and B+3 cations can be
same or different.
Oxide ion present in the spinel undergo cubic clossed packing to construct two types of
void’s known as tetrahedral void and octahedral void.
(i) If all the +2 cations are occupied in the tetrahedral voids and all the +3 cation occupied in the
octahedral voids then the spinal is known as simple or normal spinel, which can be
represented as:-
A+2 [B2+3] O4
(ii) If all the +2 cations and half of the +3 cations are occupied in the octahedral voids while the
remaining half of the +3 cations are occupied in the tetrahedral voids then the spinel is
known as inverse spinel, which can be represented as:
B+3 [A+2 B+3] O4
Now the nature of spinels can be determined with the help of CFSE for the A+2 & B+3
cations under weak field octahedral and tetrahedral conditions.

2.6.4.1 Spinel Structure of Mn3O4

INORGANIC CHEMISTRY- III

To determine the spinel structure of Mn3O4, at first we have to consider the Mn+2 and
Mn+3 ions in the octahedral and tetrahedral voids to construct the weak field octahedral and
tetrahedral complexes. Then after that we can calculate the CFSF value under weak field
octahedral and tetrahedral conditions.
Mn+2(3d5) Mn+3(3d4)
CFSE under strong field octahedral condition 0 -0.9 ∆o
CFSE under strong field tetrahedral condition 0 - 0.27 ∆o
Since, the value of CFSE for Mn+3 under weak field octahedral condition is more –ve,
which indicates that Mn+3 will have the tendency to occupied in the octahedral voids i.e. the Mn3
O4 will have simple spinel (Normal spinel) structure.
Mn3O4 → Mn2+[Mn23+]O4

2.6.4.2 Spinel structure of Fe3O4

Fe3O4 containing one of the Fe in the +2 oxidation states and 2Fe in the +3 oxidation
state. To determine the spinel structure of Fe3O4, at first we have to consider the Fe+2 and Fe+3 in
the octahedral and tetrahedral voids to construct the weak filed octahedral and tetrahedral
complexes. Then after that we can determine the CFSE tetrahedral under the weak field
octahedral and tetrahedral conditions.

Fe+2(3d6) Fe+3(3d5)
CFSE under strong field octahedral condition - 0.4 ∆o 0
CFSE under strong field tetrahedral condition -0.27 ∆o 0
Since, the value of CFSE for the Fe+2 ion under weak field octahedral condition is more
–ve, this indicates that the Fe+2 will have the tendency to occupied in the octahedral void i.e. the
i.e. the Fe2 O4 will have inverse spinal structure.
Fe3O4 Fe+3[Fe+2Fe+3]O4

2.7 LIMITATIONS OF CFT

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1. CFT considers the splitting of d- orbital but it does not consider the splitting of other orbitals
in the ligand field environment.
2. CFT can’t explain that how certain ligands having more splitting power/ability while certain
other ligands having very low splitting ability.
3. According to the CFT, metal ligand bond having 100% ionic character but from the various
experiments, it was proved that metal ligand bonds have certain extent of covalence with the
ionic character.

The crystal field theory is modified to take into account the existence of some degree of
covalence character in transition complexes based on the evidence from electron spin resonance
spectra which shows that certain percentage of the electrons is diffused into the ligand orbitals.
Consequently, the bond existing in the complexes is not purely electrostatic. The modification of
CFT results into adjusted Crystal Field Theory also called Ligand Field theory (LFT). If the
degree of diffusion or overlap is in excess, the LFT will not hold rather a pure covalent treatment
will be suitable hence, the use of Molecular Orbital theory (MOT). The LFT can be considered
as a mid-point between electrostatic and covalent description of bonding in metal complexes.
The LFT is purely a parameter based model involving the uses of experimentally derived data or
parameters like crystal field stabilization energy and Racah parameters which are derived from
electronic spectra of complexes.
Molecular Orbital Theory is the result of overlap of bonding atomic orbital of the ligands
and the hybridized orbital of the metal leading to formation of both bonding and antibonding
molecular orbitals. In a molecular bonding scheme, the numbers of bonding and antibonding
orbitals are equal but the antibonding orbitals canceled out the resultant effect of the bonding
orbitals. Molecular Orbital Theory in an octahedral complex can be illustrated with complex
[Co(NH3)6]3+ in which metal–ligand σ-bonding is dominant. In the construction of a molecular
orbital energy level diagram for such a complex, many approximations are made and the