Metal Ligand Bonding PDF

21
Metal Ligand
Bonding in Transition
Metal Complexes
2.1. INTRODUCTION
Werner is known as the Father of Coordination Chemistry. He made the first attempt to explain
bonding in coordination compounds, for which he was awarded the Nobel prize in 1913. The features
of his theory include the primary valencies and secondary valencies. Later Sidgwick extended the
theory by suggesting that the metal ions accept the electron pairs from the ligands in order to achieve
the next noble gas configuration. This was followed by the development of valence-bond theory by
Linus Pauling. Valence bond theory could explain the stereochemistry and magnetic properties of
coordination compounds (Complexes), but it had certain limitations. In this chapter, we plan to deal
in detail the Crystal Field Theory. But before that we shall have a brief
recap of valence bond theory and its limitations. We shall then explain
how crystal field theory addresses some points which are not explained
by valence bond theory. But the fact remains that in spite of the
limitations of valence bond theory, it is still the simplest theory to explain
most of the points.
2.2. VALENCE BOND THEORY

Valence bond theory assumes the bonding between metal ion and
ligands to be purely covalent. The covalent bond in metal complexes is
formed by the overlap of a filled ligand orbital containing a lone pair
of electrons with a vacant hybrid orbital of the metal atom or ion, as Linus Pauling
shown in Fig. 2.1.
M L M L
Vacant hybrid Filled orbital M L

orbital of metal of ligand Coordinate covalent
bond
Fig. 2.1. Formation of a metal-ligand bond

This theory gives appropriate explanation for the structures and magnetic properties of
coordination compounds. The salient features of this theory are :
1. The central metal atom or ion in the complex provides a number of empty orbitals for the
formation of coordinate bonds with suitable ligands. The number of empty orbitals provided is equal
to coordination number of the central metal ion.
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26 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
2. A number of s, p and d atomic orbitals of the metal hybridise to give a set of new orbitals
of equivalent energy, called hybrid orbitals. These hybrid orbitals are directed according to definite
geometry of the complex such as square planar, tetrahedral, octahedral etc.
3. The d-orbitals involved in the hybridisation may be either inner (n – 1) d-orbitals or outer
(nd) orbitals. Thus, in case of octahedral hybridisation, the orbitals may involve sp3d2 hybridisation
or d2sp3 hybridisation.
4. Each ligand has at least one orbital containing a lone pair of electrons to overlap with the
hybrid orbital of the metal.
5. The empty hybrid orbitals of metal ion overlap with the filled orbitals of the ligand to form
a covalent sigma bond (L M).
6. In addition to a sigma bond, there is also a possibility of  bond.
Some common types of hybridisation of atomic orbitals and their geometries that are involved
are given in Table 2.1.
Table 2.1. Some common types of hybridisations.
Coordination Hybridisation Shape Geometry
Number
2 sp Linear
3 sp2 Trigonal planar
4 sp3 Tetrahedral
4 dsp2 Square planar
5 dsp3 Trigonal bipyramidal
5 sp3d Square pyramidal
METAL LIGAND BONDING IN TRANSITION METAL COMPLEXES 27
6 d2sp3 or sp3d2 Octahedral
Applications of valence bond theory

We shall illustrate the valence bond theory by taking some examples of complexes.
Complexes of Coordination Number 5

1. [Cr(NH3)6]3+ complex
Chromium (Z = 24) has the electron configuration 3d5 4s1. Chromium in this complex is in
+3 oxidation state formed by the loss of one 4s and two of the 3d electrons (Fig. 2.2). The inner
d-orbitals are already vacant and two vacant 3d, one 4s and three 4p orbitals hybridise to form six
d2sp3 hybrid orbitals. Six pairs of electrons one from each NH3 molecule, occupy the six hybrid
orbitals giving octahedral geometry. There are three unpaired electrons in the complex, therefore,
we expect it to be paramagnetic.
Configuration of
3d 4s 4p
Cr
Cr (III)
d2sp3 Hybridisation
[Cr(NH3)6]3+
Fig. 2.2. Formation of [Cr(NH3)6]3+ complex involving d2sp3 hybridisation. xx represent electron
from ligands.
3+
2. [Co(NH3)6] complex
Cobalt atom (Z = 27) has the electronic configuration 3d74s2. Cobalt is in +3 oxidation state
with the electronic configuration 3d6 (Fig. 2.3). Four of the 3d orbitals are singly filled and one 3d
orbital has a pair of electrons. Octahedral complexes are formed by involving d2sp3 hybridisation.
Configuration of
3d 4s 4p
Co
Co (III)
d2sp3 Hybridisation
[Co(NH3)6]3+
Fig. 2.3. Formation of [Co(NH3)6]3+ complex ion, xx represents electron pairs from the ligands.
Therefore the metal atom must make available two of its 3d orbitals as empty. To achieve this, two
electrons in the 3d orbitals pair up with two other electrons in 3d orbitals making two 3d orbitals
empty. We expect that [Co(NH3) 6]3+ complex ion will be diamagnetic and this has been
experimentally observed to be so. Then, these six vacant orbitals comprising two 3d, one 4s and
three 4p orbitals hybridise to form six vacant d2sp3 hybrid orbitals. Six NH3 molecules donate one
pair of electrons each to these vacant hybrid orbitals. Thus, the complex has octahedral geometry
and is diamagnetic.
3. [CoF6]3– complex ion
In this complex cobalt is in +3 oxidation state with electronic configuration 3d6. This complex
has been found to be paramagnetic corresponding to four unpaired dlectrons. This means that it cannot
involve d2sp3 hybridisation because the complex in that case would be diamagnetic as [Co(NH3)6]3+.
Huggins (in 1937) solved this puzzle by suggesting that the metal can also use outer d-orbitals
for hybridisation. Therefore, in the complex ion [CoF6]3–, the 3d orbitals are not disturbed i.e. they
are not paired and the outer 4d orbitals are used for hybridisation. The six orbitals comprising one
4s, three 4p and two 4d hybridise forming six sp3d2 hybrid orbitals. Six pairs of electrons, one each
from F– ion are donated to the vacant hybrid orbitals forming coordinate bonds as shown in Fig.
2.4.
Configuration of
3d 4s 4p
Co
Co (III)
sp3d2 Hybridisation
[CoF6]3–
Fig. 2.4. Formation of [CoF6]3– complex. xx represents electron pair donated by the ligands.
We note that in octahedral complexes the central metal may use inner (n —1)d orbitals in some
cases and outer nd orbitals in other cases for hybridisation. Correspondingly, we use the terms inner
orbital complex and outer orbital complex.
In the formation of inner orbital complex, the electrons of the metal to pair up and hence the
complex is expected to be either diamagnetic or will have lesser number of unpaired electrons. Such
a complex is called low spin complex. On the other hand, the outer orbital complex is expected
to have a larger number of unpaired electrons. Such a complex is called high spin complex.
4. [Fe(CN)6]3– complex
Iron atom (Z = 26) has the electronic configuration 3d64s2. In this complex, iron is in +3
oxidation state and has the electronic configuration 3d5 (Fig. 2.5). The compound has magnetism
corresponding to one unpaired electron. To achieve this the two electrons in 3d orbitals pair up
leaving two 3d orbitals empty. These six vacant orbitals comprising two 3d, one 4s and three
4p orbitals hybridise to form d2sp3 hybrid orbitals. Six pairs of electrons one from each CN– ion
are donated which occupy the six vacant hybrid orbitals of the metal. The molecule has octahedral
geometry and is paramagnetic due to the presence of one unpaired electron.
Configuration of
3d 4s 4p
Fe
Fe (III)
d2sp3 Hybridisation
[Fe(CN)6]3–
Fig. 2.5. Formation of [Fe(CN)6]3– complex involving d2sp3 hybridisation.

5. [Fe(H2O)6]3+ ion
In this case also, iron is in +3 oxidation state and has the electronic configuration as 3d5 (Fig.
2.6). This complex has been found to be paramagnetic corresponding to five unpaired electrons.
We explain it by assuming that the electrons in 3d-orbitals are not disturbed and the outer 4d orbitals
are used for hybridisation. As in the case of [CoF6]3– the six orbitals (one 4s, three 4p and two 4d)
hybridise (sp3d2) forming six hybrid orbitals oriented along the corners of an octahedron. Six pairs
of electrons, one from each water molecule occupy the six hybrid orbitals. The molecule is
octahedral and is paramagnetic, as explained by Fig. 2.6.
Configuration in
3d 4s 4p
Fe
Fe (III)
sp3d2 Hybridisation
[Fe(H2O)6]3+
Fig. 2.6. Formation of [Fe(H2O)6]3+ complex involving sp3d2 hybridisation.
Complexes of coordination number 4

There are two ways in which the complexes of coordination number 4 can be formed. If the
hybridisation involved is sp3, we get tetrahedral complexes with the ligands situated at the corners
of a tetrahedron. On the other hand, if the hybridisation involved is dsp2, we get square planar
complexes with four ligands occupying four corners of a square. Some examples are discussed
below:
1. [Ni(CN)4]2– ion
The nickel atom has the ground state electronic configuration as 3d8 4s2. In this case nickel
is in +2 oxidation state and its electronic configuration is 3d8 (Fig. 2.7).
The experiments show that the complex [Ni(CN)4]2– is diamagnetic (no unpaired electron)
indicating that the hybridisation involved in this case is dsp2 as represented in Fig. 2.7. Two electrons
in 3d orbitals pair up to make available one empty 3d orbital for dsp2 hybridisation. Consequently,
the structure of the complex would be square planar. The empty hybrid orbitals of the metal overlap
with the orbitals of cyanide ions, to form metal-ligand coordinate bonds.
Configuration of
3d 4s 4p
Ni
Ni (II)
dsp2 Hybridisation
[Ni(CN)4]2–
Fig. 2.7. Formation of square planar complex, [Ni(CN)4]2– involving dsp2 hybridisation.
2. [NiCl4]2– ion
The nickel (II) ion has two unpaired electrons, as shown in Fig. 2.8. The magnetic
measurements of the complex [NiCl 4]2– show that it is paramagnetic and has two unpaired
electrons. Therefore, in this case the 3d-orbitals remain undisturbed and sp3 hybridisation occurs
resulting in tetrahedral structure of the complex. Threre are two unpaired electrons in the complex,
therefore it is paramagnetic.
Configuration of
3d 4s 4p
Ni
Ni (II)
sp3 Hybridisation
[Ni(Cl)4]2–
Fig. 2.8. Formation of tetrahedral [NiCl4]2– complex involving sp3 hybridisation.

3. [Ni(CO)4]
The nickel (0) has 3d84s2 as its outer electronic configuration (Fig. 2.9). The magnetic studies
of the complex [Ni(CO)4] show that the complex is diamagnetic (no unpaired electrons). This
indicates that the two electrons in the 4s-orbital are forced to pair up with the 3d-orbitals. Thus sp3
hybridisation takes place and the complex has tetrahedral structure.
Configuration of
3d 4s 4p
Ni
Ni (0)
sp3 Hybridisation
[Ni(CO)4]
Fig. 2.9. Formation of tetrahedral [Ni(CO)4] complex, xx represents

electron pair donated by ligands.
4. [Cu(NH3)4]2+ ion
The oxidation state of copper in this complex ion is +2. Therefore, it has 3d9 outer
configuration (Fig. 2.10). X-ray studies show that this complex ion has a square planar geometry.
Therefore, the metal ion must involve dsp2 hybridisation and one of the 3d orbital must be vacated.
This can be achieved by promoting one electron from one of the 3d orbitals into higher energy
vacant 4p orbitals. But if the electron occupies higher energy level, it will be easily lost. This means
that the complex could be easily oxidised, i.e. Cu2+ will change into Cu3+. However, this does not
happen because Cu3+ ions are rare. The spectroscopic studies have also shown that electron is not
present in the 4p orbital. To solve the anomaly, it has been suggested that the electrons in 3d orbitals
remain undisturbed and it involves the use of outer 4d orbitals for hybidisation. Thus, this complex
is square planar involving sp2d hybrid orbitals.
Configuration of
3d 4s 4p
Cu
Cu (II)
sp2d Hybridisation
4d
2+
[Cu(NH)3]
Fig. 2.10. Formation of [Cu(NH3)4]2+ complex. xx denotes electrons donated by the ligands.
Limitations of valence bond theory

Although valence bond theory has radically improved our understanding of complex
compounds still it suffers from many limitations. The main limitations of valence bond theory are:
1. It does not explain the electronic spectra of complexes.
2. It does not predict the relative stabilities of different complexes. Certain complexes are labile
in which the displacement of ligand takes place rapidly, while some are inert in which ligand
displacement by another ligand is very slow. Valence bond theory does not explain this.
3. It does not explain the colour of complexes.
4. The valence bond theory does not tell us why water and halide ions commonly form high
spin complexes while cyanide ions form low spin complexes.
5. This theory does not explain as to why in some cases inner orbitals and in other cases outer
orbitals are used in hybridisation.
6. It is unable to predict the relative stabilities of different
ligands.
7. It does not take into account the splitting of d-energy levels.
2.3. CRYSTAL FIELD THEORY (CFT)

The crystal field theory was developed by H. Bethe and V.
Bleck. This theory is based on the assumption that the metal ion
and the ligands act as point charges and the interactions
between them are purely electrostatic. In case of negative ligands
(anions such as Cl–, Br–, CN–), the interactions with metal ions are
ion - ion interactions. If the ligands are neutral molecules (such as H. Bethe
NH3, H2O, CO), the interactions with the metal ion are ion-dipole interactions. For example, in
the case of complex ion [CoF6]3– the interactions are between Co3+ and F– ions whereas in
[Co(NH3)6]3+, the interactions are between negatively charged pole of NH3 molecule and Co3+ ion.
This is in contrasts the valence bond theory which considers bonding between the metal and ligands
as covalent.
The electrons of the metal ion in the environment of ligands within the lattice of a crystal are
affected by the non-spherical electric field established by the ligands. The electric field was called
the crystalline field, but now, it is called as crystal field. This is how the theory derived its name.
Basic assumptions (features) of crystal field theory

1. The transition metal ion is surrounded by the ligands with lone pairs of electrons.
2. All types of ligands are
regarded as point charges. The ligands
may be either ionic like F–, Cl–, CN–,
etc. or molecules such as H2O, NH3,
CO, etc. If the ligand happens to be a
neutral molecule, then the negative end
of the dipole is oriented towards the
metal ion. For example, ammonia, NH3
is polar molecule having -negative
charge on N and + charges on H
atoms. Similarly, water is also polar
with -charge on O and + charges on
H atoms.
3. The interactions between the
metal ion and the negative ends of Crystal field
anion or ligand molecule is purely
electrostatic, i.e. the bond between the metal and ligand is considered 100% ionic.
4. The ligands surrounding the metal ion produce electrical field which influences the energies
of the d-orbitals of central metal ion. In a free metal ion, all the five d-orbitals have the same energy.
These orbitals having the same energies are called degenerate orbitals. This means that an electron
can occupy any one of these five d-orbitals. However, on the approach of the ligands, the orbital
electrons are repelled by the lone pairs of the ligands. The repulsion raises the energy of the d-
orbitals. Now d-orbitals have different orientations and, therefore, these d-orbitals will experience
different interactions from the ligands. The orbitals lying in the direction of the ligands, will
experience greater repulsion and their energies will be raised to greater extent. On the other hand,
the orbitals not lying along the approach of the ligands will face smaller interactions and therefore,
their energies will be raised to lesser extent.
5. Due to the electrical field of the ligands, the energies of the five d-orbitals will split up. This
conversion of five degenerate d-orbitals of the metal ion into different sets of orbitals having
different energies in the presence of electrical field of ligands is called crystal field splitting. This
concept forms the basis of crystal field theory.
6. We can explain the magnetic properties, spectra and preference for particular geometry in
terms of splitting of d-orbitals in different crystal fields.
7. The number of ligands (coordination number) and their arrangement (geometry) around the
central metal ion will have different effect on the relative energies of the five d-orbitals. In other
words, the crystal field splitting will be different in different structures with different coordination
numbers.
To understand the crystal field theory, it is essential to have a clear picture of the orientation
of the five d-orbitals in space and the geometrical arrangement of the ligands around the central
metal ion. We shall consider the complexes with coordination number 6 and 4, which are very
common, to make the theory understandable.
Shapes of d-orbitals
There are five d-orbitals. These are designated as d xy , d yz , d zx , d x 2  y 2 and d z 2 . The shapes
of these orbitals are given below:
(i) The three orbitals dxy, dyz and dzx are similar and each of them consists of four lobes of
high electron density lying in xy, yz and zx planes respectively. These lobes lie in between the
principal axes. For example, in case of dxy orbital, the four lobes lie in xy plane in between the x
and y-axes (Fig. 2.11).
(ii) The d x 2  y 2 orbital also has four lobes of high electron density along the x-axis and y-axis.
It may be noted that this orbital is exactly like dxy orbital except that it is rotated through 45°
around the axis.
(iii) The d z 2 orbital consists of two lobes along the z-axis with a ring of high electron density
in the xy plane.
x z z
y y x
dyz dzx
y z
x x
dx2 – y2 dz2
Fig. 2.11. Shapes of five 3d orbitals.

There is some thing interesting to be noted about d z 2 and d x 2  y 2 orbitals. Although d z 2 and
d z 2  y 2 orbitals do not look to be similar yet they are equivalent so far as interactions with the metal
ions are concerned. The d z 2 orbital may be regarded as a linear combination of two orbitals d z 2  x 2
and d z 2  y 2 , each of which is equivalent to the d x 2  y 2 orbital as shown in Fig. 2.12.
z z z
+ + y +
–
– – x + x x
–
+ + y +
dz2 – x2 dz2 – y2 dz2
Fig. 2.12. Representation of z2 orbital as a linear combination of d z 2  x 2 and d z 2  y 2 orbitals.
However, these two orbitals ( d z 2  x 2 and d z 2  y 2 ) do not have independent existence and the
d z 2 orbital can be thought of as having the average properties of the two.
Crystal field Splitting in octahedral complexes (Coordination number 6)

In an octahedral complex the metal ion occupies the centre of the octahedron and the ligands
are situated at the six corners as shown in Fig. 2.13. The three axes X, Y and Z point along the
corners of the octahedron. Suppose the metal ion, Z
Mn+, possesses a single d-electron (d1 configuration,
e.g. Ti3+ in [TiF6]3–). In the free ion, when there are
no ligands, the electron can occupy any one of the
five d-orbitals because all are of the same energy.
However, in the octahedral complex MX6, all n+
M X
the five d-orbitals will no longer be of equal energy.
The arrangement of d-orbitals shows that the two
lobes of d z 2 orbitals and four lobes of d 2 2 x y
orbital point directly towards the corners of the
Y
octahedron, where the negative charges of the ligands
are concentrated. The remaining three orbitals are Fig. 2.13. Six ligands at the corners of an
oriented in between the axes (Fig. 2.14). In the case octahedron surrounding the metal ion, Mn+.
of octahedral complexes, the former two orbitals are designated as eg orbitals while the latter three
orbitals are designated as t2g orbitals. As the two ligands approach the central ion along the axes,
the eg orbitals are repelled more than the t2g orbitals. In other words, the energy of the d z 2 and
d x 2  y 2 orbitals increases much more than the energy of the dxy, dyz and dzx orbitals. Greater the
repulsion between similar charges, greater is the increase in energy.
Z Z
X X
Y
dz2 dx2 – y2
eg– orbitals
Z Z Z
X X X
Y Y Y
dxy dyz dzX
t2g– orbitals
Fig. 2.14. Orientations of different d-orbitals in an octahedral field of six ligands.
Thus, in octahedral complexes, the five d-orbitals split up into two sets : one set consisting
of two orbitals of higher energy (eg orbitals) and the other set consisting of three orbitals of lower
energy ( t2g orbitals). This represents crystal field splitting in an octahedral complex (Fig. 2.15).
eg
0.6 0 or 6 Dq
0 or 10 Dq
0.4 0 or 4 Dq
Energy
t2g
Free ion Energy of orbitals in Splitting of orbitals

spherical field of ligands in octahedral field
(a) (b) (c)
Fig. 2.15. Crystal field splitting in an octahedral complex.

The energy difference between two sets of d-orbitals; t2g and eg is called crystal field splitting
energy and is symbolically represented as 0 (The subscript (0) for octahedral). The magnitude of
0 varies for different complexes. The crystal field splitting is also measured in terms of another
parameter called Dq. The two units are related as :
0 = 10 Dq
It may be noted that the crystal field splitting occurs in such a way that the average energy of
the d-orbitals does not change. This is known as barycentre rule, which is similar to ‘centre of
gravity’ type rule. This requires that the decrease in energy of the set of orbitals that lie at the lower
energy level must be balanced by the corresponding increase in other set. Therefore, in terms of
total energy 10 Dq, the energy of each of the two eg orbitals is raised by 6 Dq and the energy of
each of the three t2g orbtials is lowered by 4 Dq. In terms of 0, the energy of each of the two eg
orbitals is raised by 3/5 0 (or 0.6 0) and the energy of each of the three t2g orbitals is lowered
by 2/5 0 (or 0.4 0).
The values of 10 Dq or O are obtained spectroscopically. Initially the energies of all the five
d-orbitals are raised equally (state II) if the field created by the ligands were spherically symmetrical
(Fig. 2.15 b). However, the energies of d-orbitals split into two sets because of the different
orientation of the orbitals towards the ligands (Fig. 2.15 c). Fig. 2.15 a represents the energy of
orbitals in free metal ion.
Crystal Field Stabilization Energy (CFSE)

In an octahedral field, the energies of five d-orbitals split up. Three orbitals are lowered in
energy (t2g) while two orbitals are raised in energy (eg). Also the electrons always prefer to occupy
an orbital of lower energy. In the case of d1 system, the d-electron will prefer to occupy a t2g orbital
and is, therefore, stabilized by an amount equal to 0.4 0 or 4 Dq. The amount of stabilization
provided by splitting of the d-orbitals into two levels is called crystal field stabilization energy
(CFSE). Thus, in octahedral field for each electron that enters the t2g orbtial, the crystal field
stabilization is –4 Dq and for each electron that enters the eg orbital the crystal field destabilization
energy is +6 Dq. We can calculate CFSE for octahedral complexes for different d-orbital
configurations.
CFSE for various octahedral complexes

(i) For a d1 system (e.g. Ti3+ ion) the electron will be present in any one of the three t2g orbitals.
The electronic configuration may be written as t2g1.
CFSE = 1(–4 Dq) = –4Dq
(ii) For a d2 system (e.g. V3+ ion) the electrons will occupy t2g orbitals with their spins parallel
in accordance with Hund’s rule. The electronic configuration is t2g2.
CFSE = 2(–4 Dq) = –8Dq
(iii) For a d3 system (e.g. Cr3+), the electronic configuration is t2g3.
CFSE = 3(–4 Dq) = –12Dq
(iv) For a d4 system (e.g. Mn3+ ion), there are two possibilities :
(a) All the four electrons may occupy t2g orbitals with one electron getting paired with
electronic configuration t2g4.
(b) Three electrons occupy t2g orbitals and the fourth electron goes to one of the eg orbitals
giving the configuration t2g3 eg1.
There are two factors that decide the configuration, the CFSE o and the pairing energy P.
While 0 is difference of energy between eg and t2g orbitals, P is the pairing energy. It is the energy
required to pair two electrons together.
The configuration (a) is possible if o > P. These complexes are called strong field complexes
because o is large. In this case, the complex has less number of unpaired electrons and is called
low spin complex. The configuration (b) is possible if  o < P. It is called weak field and the
eg eg
High spin
Low spin o
o complex
complex
t2g
t2g
Strong field
(0 > P)
complexes are called weak field complexes. In that case, the maximum number of electrons remain
unpaired and the complex is called high spin complex. Electrons tend to enter the orbital with
smaller energy or involving smaller energy changes. If greater energy is involved in moving to the
higher eg orbital, they prefer to pair within the t2g orbital. On the other hand, if greater energy is
involved in pairing of electrons, they prefer to occupy higher energy eg orbital.
Thus, for a low spin complex having t2g4 configuration,
CFSE = 4(– 4 Dq) = – 16 Dq
To be precise, we should take into account pairing energy (P) also. Therefore,
Net CFSE = – 16 Dq + P
For a d high spin complex, having the configuration t2g3 eg1 :
4
CFSE = 3(– 4 Dq) + 1(6 Dq) = – 6 Dq.

(v) For a d5 system (e.g. Fe3+ ion) again there are two possibilities :
(a) All the five electrons may occupy t2g orbitals with two orbitals getting paired. The
electronic configuration may be written as t 2g5. This is possible if 0 > P and the
complex will be called strong field or low spin complex.
(b) The three electrons occupy t2g orbitals and two electrons occupy e g orbitals. The
electronic configuration may be written as t2g3eg2. This will be possible if 0 < P and
the complex is called weak field or high spin complex.
The CFSE in these two types of complexes will be :
(a) Strong field :  o > P
CFSE = 5(– 4 Dq) + 2P

= – 20 Dq + 2P
(b) Weak field :  o < P
CFSE = 3(– 4 Dq) + 2(6 Dq)

=0
The CFSE for metal ion for different dn configurations are given in Table 2.2. It may be noted
that d8, d9 and d10 systems have only one possible configuration.
Table 2.2. Crystal field stabilization energies for metal ions having different numbers of
d-electrons in octahedral complexes.
(Values for weak and strong fields are given separately where applicable)
Number of Weak field CFSE Strong field CFSE

electrons
d1 – 4 Dq
or
– 0.4 0
d2 – 8 Dq
or
– 0.8 0
d3 – 12 Dq
or
– 1.2 0
d4 – 6 Dq – 16 Dq + P
or or
– 0.6 0 – 1.6 0 + P
d5 – 20 Dq + 2P
0 or
– 2.0 0 + 2P
d6 – 4 Dq – 24 Dq + 2P
or or
– 0.4 0 – 2.4 0 + 2P
d7 – 8 Dq – 18 Dq + P
or or
– 0.8 0 – 1.8 0 + P
d8 – 12 Dq – 12 Dq
or or
– 1.2 0 – 1.2 0
d9 – 6 Dq
or
– 0.6 0
d10
0
The systems d1, d2, d3, d9 and d10 have same configuration in weak field and strong field and,
therefore, have same CFSE values.
Crystal field splitting in tetrahedral complexes (Coordination number 4)

The tetrahedral arrangement of four ligands surrounding a metal ion may be visualized by
placing on the four of the eight corners of the cube (Fig. 2.16). The directions X, Y and Z point to
the centre of the faces of the cube. From the figure, we find that the orbitals dxy, dyz and dzx point
between X, Y and Z-axis (i.e. towards the

centre of the edes of the cube) whereas the
orbitals t x 2  y 2 and d z 2 point along X, Y
and Z axis (i.e. to the centres of the faces).
Clearly in the tetrahedral field, none of the
d-orbitals point exactly towards the
ligands and therefore, smaller splitting of
energy will take place compared to that in
octahedral field. The three d-orbitals dxy,
dyz and dzx point close to the direction in
which the ligands are approaching while
the two orbitals d x 2  y 2 and d z 2 lie in
between the ligands. Therefore, the
Crystal field splitting
energies of the three orbitals will be raised
while the energies of the two orbitals will be lowered. Thus, in the presence of tetrahedral field,
the splitting of d-orbitals will take place as under.
(i) The two orbitals, d x 2  y 2 and d z 2 become stable and their energies are lowered. These are
designated as e orbitals.
(ii) The three orbitals dxy, dyz and dzx become unstable and their energies are raised. These are
designated as t2 orbitals.
Z
n+
M X
Fig. 2.16. Tetrahedral field of four ligands around the central metal ion.
A point of distinction between splitting of d-orbitals in tetrahedral and octahedral fields is that
‘g’ is not used. For example, the orbitals d x 2  y 2 and d z 2 are designated as e orbitals whereas the
other three orbitals dxy, dyz and dzx are designated as t2. This is because a tetrahedral geometry has
no centre of symmetry. The symbols g and u have relevance only for fields which have centre of
symmetry.
Splitting of d-orbitals in tetrahedral field is shown in Fig. 2.17.
The magnitude of crystal field splitting which is the difference between e and t2 orbitals is
designated as t (the subscript t indicating tetrahedral complexes). It is also measured in terms of
Dq as
t = 10 Dq
t2
4 Dq
t or 10 Dq
6 Dq
Energy
e
Free ion Energy of d orbitals in Splitting of orbitals
spherical field of ligands in tetrahedral field
Fig. 2.17. Crystal field splitting in a tetrahedral field.

It has been observed that the crystal field splitting in tetrahedral complexes (t) is much less
than in octahedral complexes (o). The relation between the two (for the same metal ion and ligands)
is
4
t = o
9
There are two main reasons for the smaller value of t than o
(i) In tetrahedral complexes there are four ligands while there are six ligands in octahedral
complexes. Therefore, lesser ligands produce less crystal field splitting. On this account
crystal field splitting in tetrahedral field is about two third of the octahedral field.
(ii) Further in tetrahedral field, none of the orbitals is pointing directly towards the ligands and,
therefore, splitting is less.
4
Precisely t = o
9
There is an interesting point to be noted in splitting in tetrahedral field. The magnitude of
crystal field splitting in tetrahedral field is quite small and is always less than the pairing energy.
Therefore, we do not expect the pairing of electrons to take place. Thus, all the tetrahedral
complexes are high spin complexes.
CFSE for tetrahedral complexes

Average energy of the d-orbtials does not change (barycentre rule). Therefore, in terms of 10
Dq the energy of each of the e orbital is lowered by 6 Dq and the energy of each of the t2 orbital
is raised by 4 Dq. In terms of t, the energy of each e orbital is lowered by 3/5 t (or 0.6 t) while
each of the t2 orbital is raised by 2/5 t (or 0.4 t). We calculate the value of t for different
configurations as under.
(i) For d1 system, the electronic configuration is e1.
CFSE = 1(– 6 Dq) = – 6Dq
(ii) For d2 system, the electronic configuration is e2.
CFSE = 2(– 6 Dq) = – 12Dq
(iii) For d3 system, the electronic configuration is e2 t21. As already discussed, crystal field
splitting in tetrahedral field is quite small and is always less than the pairing energy. Therefore,
pairing does not occur and most of the complexes are high spin complexes, whether it is a weak
field or a strong field.
CFSE = 2(– 6 Dq) + 1(4 Dq) = – 8Dq
The CFSE for compelxes with metal ion having different configurations of d-orbitals in
tetrahedral field are given in Table 2.3.
Table 2.3. Crystal field stabilization energies for tetrahedral complexes with metal ions for
different dn.
d1 CFSE = – 6Dq d2 CFSE = – 12Dq
d5 CFSE = 0 d6 CFSE = – 6Dq
d9 CFSE = – 4Dq d 10 CFSE = 0
Precisely, the pairing energy values should also be taken into consideration. However, to
simplify the matter, these have been omitted here.
Crystal field splitting in tetragonal and square planar complexes

Let us first clarify what we mean by tetragonal and square planar complexes. When all the
ligands are equidistant from the central metal ion, it is a case of octahedral complex (Fig. 2.13.)
However, if some ligands, say two ligands along z-axis are at a different length, then it will become
a case of tetragonal complex. In square planar complexes, the four ligands are situated at the corners
of a square.
The splitting of d-orbitals in tetragonal and square planar complexes can be visualised from
the known splitting of d-orbitals in octahedral complexes. This is because tetragonal and square
planar geometries can be understood by stretching or withdrawing two trans ligands from an
octahedral complex. This process is called elongation. Generally, we consider the stretching or
removal of trans ligands along the Z-axis.
As the ligands lying on the Z-axis are moved away, the ligands in the XY plane are drawn
closer to the central ion. Due to increase in metal ligands bond along Z-axis, the repulsions from
the ligands to electrons in d z 2 orbital decreases and therefore, the energy of dz2 obital is decreased
relative to that in octahedral field. At the same time, the metal ligand bond along X and Y are
shortened so that the d-orbital in XY plane, d x 2  y 2 experiences greater repulsion from the ligands
and therefore, its energy is raised. Similarly, the dxz and dyz orbitals are lowered in energy because
of decrease in repulsion effects along the Z-axis while the energy of dxy orbital is raised. The
resulting splitting considering the above forces is shown in Fig. 2.18. This state represents
tetragonally distorted octahedral structure.
dx2 – y2
eg dx2 – y2
sp
dxy
Energy
dz2
dz2
dxy
t2g
Octahedral
Structure dyz dzx
Tetragonal
dyz dzx
structure
Square Planar
Fig. 2.18. Crystal field splitting in octahedral, tetragonal and square planar complexes.
When the trans ligands lying along Z-axis are completely removed, a square planar complex
is formed. In the square planar complex, the energies of d x 2  y 2 and dxy orbitals rise further and
energies of d z 2 , d xz and dyz orbitals fall further as shown in Fig. 2.18. It has been observed that
L L
L
L M L L M L L M L
L
Square planar
Tetragonal (Trans ligand are
L (two trans ligands are L completely removed)
at large distance)
Fig. 2.19. Sequence of change of octahedral geometry to tetragonal and finally to square planar
geometry by removing two trans ligands.
in square planar complex, the energy of d z 2 orbital falls even below the dxy orbital. The change
of an octahedral complex to tetragonally distorted octahedron and finally to square planar
arrangement is shown in Fig. 2.19.
Tetragonally distorted structure can be obtained in two ways, by pulling apart trans ligands
from the metal ion and by bringing the trans ligands closer to the metal ion Fig. 2.20 (a) shows
elongation of octahedron. In flattening of octahedron (Fig. 2.20 (b), the two trans M—L bonds are
shortened while other four M–L bonds become large. The splitting of energies of d-orbitals will be
reverse of that in the case of elongation.
L Metal-Ligand
bond a > b L Metal-Ligand
bond a < b
a a
b b
L b b L L b b L
M M
b b
a a
L
L
(a) Elongation (b) Flattening
Fig. 2.20. Tetragonally distorted octahedron (a) elongation (b) flattening.
Crystal field theory and magnetic properties of complexes

Crystal field theory has helped understand the magnetic properties of coordination compounds
in a sound manner. The substances which have all paired electrons are called diamagnetic while the
substances which contain unpaired electrons are called paramagnetic substances. The number of
unpaired electrons, in a given complex of known geometry can be easily predicted if we know
whether the complex is low spin or high. Magnitude of 0 and pairing energy P play an important
role in this direction.
(i) If P > 0, the electrons will not pair up and the complex will be high spin complex.
(ii) If 0 > P, the electrons will prefer to pair up and the complex will be low spin complex.
Thus, the complexes with weak ligand field are high spin complexes (paramagnetic) and
those with strong ligand field are low spin complexes (diamagnetic or low magnetic character).
This generalisations could not be provided by valence bond theory. Consider the following
two complexes of cobalt (III). From experiments, it has been observed that the complex
[Co(NH3)6]3+ is diamagnetic while the complex [CoF6]3– is paramagnetic.
eg
eg
0 Large0 value
0 Small0 value
t2g
3– 3+
[CoF6] [Co(NH3)6]
High spin complex Low spin complex

(Paramagnetic) (Diamagnetic)
Fig. 2.21. Crystal field splitting and explanation for [CoF6]3– and [Co(NH3)6]3+ complexes.
Cobalt in [Co(NH3)6]3+ and [CoF6]3– is in +3 oxidation state and it has d6 configuration. It

has been observed that F– ion is a weak field ligand and therefore o is small. Therefore, o will
be less than P and the electron will remain unpaired as far as possible. This is obviously because
greater energy is required in pairing and smaller energy is required in moving to orbital of higher
Table 2.4. CFSE ( o) and pairing energies (P) for some complexes.
Complex Configuration  o (cm–1) P (cm–1) High spin/low spin
[CoF6]3– d6 13000 21000 high spin
[Co(NH3)6]3+ d6 23000 21000 low spin
[Fe(H2O)6]2+ d6 10400 17600 high spin
[Fe(CN)6]4– d6 32850 17600 low spin
Table 2.5. Number of unpaired electrons for octahedral and tetrahedral complexes.
L.S = Low spin, H.S. = High spin
No. of unpaired
No. of unpaired
Configuration
Octahedral Tetrahedral
Electronic
electrons
electrons
t2g eg e t2
d1 1 1
d2 2 2
d3 3 3
d4 L.S. 2 4
H.S. 4
d5 L.S. 1 5
H.S. 5
d6 L.S. 0 4
H.S. 4
d7 L.S. 1 3
H.S. 3
d8 2 2
d9 1 1
d10 0 0
energy. The complex will be high spin. As seen from Fig. 2.21 (a), the complex is paramagnetic
due to the presence of four unpaired electrons. On the other hand, NH3 is a strong field ligand and
therefore, o will be greater than P. As a result, the electrons pair up and this results in a low spin
complex. This is because smaller energy is required in pairing and greater energy is required in
moving to orbital of higher energy. This happens in the case of [Co(NH3)6]3+, as represented in Fig.
2.21 (b). The crystal field splitting energies (o) and pairing energies for some complexes are given
in Table 2.4.
We can estimate the number of unpaired electrons in a given complex if we know whether the
complex is a High spin (H.S.) or a Low spin (L.S.) complex. The number of unpaired electrons for
tetahedral and tetrahedral complexes for different configurations are given in Table 2.5. for
tetrahedral complexes, only high spin complexes have been considered because Dt is always Less
than P.
1.4. FACTORS DETERMINING THE MAGNITUDE OF CRYSTAL

FIELD SPLITTING
A number of factors influence the magnitude of crystal field splitting. These are discussed as
under:
1. Nature of the ligand (spectrochemical series)
Greater the ease with which the ligands can approach the metal ion, greater will be the crystal
field splitting caused by it.
(i) Small ligands can cause greater crystal field splitting because they can approach the metal
ion closely. For example, F– ion causes greater splitting and gives higher o value than large Cl–
and Br– ions.
(ii) The ligands containing easily polarizable electron pair will be drawn more closely to the
metal ion and cause greater splitting.
(iii) The ligands which have greater tendency to form multiple bonds such as CN– and NO2–
cause greater crystal field splitting. High crystal field splitting produced by CN– ligand is attributed
to the  bonding in metal. The metal donates electrons from a filled t2g orbital into the vacant orbital
on the ligand forming a stable metal-ligand bond.
(iv) The following pattern of increasing  donation is observed :
halide donors < O donors < N donors < C donors
Table 2.6 gives the crystal field splitting (o) with different ligands attached to Cr (III).
Table 2.6. Crystal field splitting with different ligands attached to Cr(III)
Complex Ligand Donor atom  0(cm–1)
[CrCl6]3– Cl– Cl 13640
[CrF6]3– F– F 15200
[Cr(H2O)6 ]3+ H2O O 17830
[Cr(NH3)6 ]3+ NH3 N 21600
[Cr (en)3 ]3+ en N 21900
[Cr(CN)6 ]3– CN– C 26280
The ligands are arranged in increasing order of crystal field splitting  as given below. This
regular order is called spectrochemical series.
Weak field ligands

I– < Br– < Cl– < NO3– < F– < OH– < ox2– < H2O < EDTA < py  NH3 < en < dipy < o-phen
< NO2– < CN– < CO
Strong field ligands
– – – – –
Thus CO, CN and NO2 are strong field ligands whereas I , Br and Cl are weak field ligands.
2. Oxidation state of the metal ion

This is another factor controlling the magnitude of the crystal field splitting. The metal ion
with higher oxidation state causes larger crystal field splitting than with lower oxidation state. For
example, the crystal field splitting energy o for [Co(H2O)6]3+ complex in which the oxidation state
of cobalt is +3, is 18,600 cm–1, whereas for the complex [Co(H2O)6]2+ in which the oxidation state
of Co is +2, o = 9,300 cm–1.
Crystal field splitting energies (o) for hexaaqua complexes of M2+ and M3+ ions are given
in Table 2.7.
Table 2.7. Crystal field splitting for hexaaqua complexes of M2+ and M3+ ions
Metal ion Oxidation state  o (cm–1) Oxidation state  o (cm–1)
V II 11800 III 18000
Cr II 13900 III 17830
Mn II 7800 III 21000
Fe II 10400 III 13700
Co II 9300 III 18600
3. Type of d-orbitals (transition series)

The extent of crystal field splitting for similar complexes of a metal in the same oxidation state
increases by about 30 to 50% on going from 3d-series to 4d series. The increase is almost of the
same amount (30–50%) on going from 4d-series to 5d-series.
This is because 4d-orbitals being bigger extend more into space in comparison to 3d-orbitals.
As a result, the 4d-orbitals can interact more strongly with the ligands resulting in greater crystal
field splitting. On similar considerations 5d orbitals of the metal ion produce greater crystal field
splitting than the 4d orbitals. This is supported by Table 2.8 which gives CFS for the second
transition series metals.
Table 2.8. Crystal field stabilisation energies for second transition series metals
Complex ion Electronic configuration  o (cm–1)
[Co(NH3)6]3+ 3d6 23,000
[Rh(NH3)6]3+ 4d6 34,000
[Ir(NH3)6]3+ 5d6 41,000
4. Geometry of the complex

We have seen earlier that the crystal field splitting energy of tetrahedral complexes (t) is much
lower the value (o) for octahedral complexes (t  4/9 o) due to smaller metal-ligand interactions.
The value of splitting energy for tetrahedral complexes, in general, is small as compared to the
pairing energy P. The tetrahedral complexes are, therefore, mostly high spin complexes.
2.5. COLOUR OF TRANSITION METAL COMPLEXES

The transition metals have the property to absorb certain radiations from the visible region
of the spectrum and as a result, the transmitted or reflected light shows complementary colour. The
visible light consists of radiations of different wavelengths ranging from blue (about 400 nm) to
red (about 700 nm). If a substance absorbs blue light, then it appears to us to be red (red is
complementary colour of blue light).
In the case of transition metal complexes, the energy difference between t2g and eg sets of d-
orbitals is small. When visible light falls on them, the electron gets raised from lower set of orbitals
to higher set of orbitals by absorbing light of some wavelength. As a result of absorption of some
selected wavelength of visible light corresponding to energy difference between the two energy
levels, the transmitted light gives colour to complexes.
The amount of energy absorved can be calculated from the relation,
hc
E = h =

where c in the velocity of light and h is Planck’s constant. We shall explain it by taking the example
of the complex [Ti(H2O)6]3+. This complex is purple.
Wavelength Å
3000 4000 5000 6000 7000
3000 20000 10000

–1
Frequency (cm )
Fig. 2.22. Absorption spectrum of [Ti(H2O)6]3+.

In this complex, the metal ion has d1 configuration. In ground state this electron occupies one
of the t2g orbitals. The visible spectrum of [Ti(H2O)6]3+ is shown in Fig. 2.22. We can see from
the figure that absorption takes place at 5000 Å or 20,00 cm–1. The energy corresponding to this
wavelength can easily be calculated as :
N 0 hc
E = N0 h =

where N0 = Avogadro number, h = Planck’s constant, c = Velocity of light
6.023  1023  6.626  1034  3.0  108

E = (S.I. units)
5000  1010
= 239 kJ mol–1
This corresponds to o for [Ti(H2O)6]3+ complex ion.
The colours corresponding to this wavelength are green and yellow lights which are absorbed
from the white light, while the blue and red poritons are emitted. The solution of complex
[Ti(H2O)6]3+, therefore, looks purple.
The difference between t2g and eg orbitals in octahedral complexes depends on the metal ion
and the nature of the ligands. Therefore, different complexes absorb different amounts of energies
from visible region and transmit different colours.
That is why [Co(H2O)6]3+ absorbs orange colour and appears blue and [Co(CN)6]3– absorbs
violet colour and appears as yellow.
Colour of copper sulphate

(i) Copper sulphate hydrated CuSO4.5H2O may be considered as a complex compound with
five water molecules as ligands. Copper is present as Cu2+ in this compound, with d9 configuration.
In the presence of ligands, the d-orbitals are split into two types t2g and eg. The filling of orbitals
is shown in Fig. 2.23.
eg
t2g
Fig. 2.23. Arrangement of electrons in t2g and eg orbitals of Cu2+.

When visible light falls on solid CuSO4.5H2O or its solution, one of the electrons in t2g is
excited to eg orbital, absorbing red region of white light. It transmits the blue colour and hence looks
blue.
(ii) Cuprous Compounds like Cu2SO4 or Cu2Cl2 (Cu+) have d10 configuration. All the d-
orbitals are completely filled. There is no possibility of excitation of electrons. It may be noted that
cuprous salts are not hydrated. Thus, there are no ligands and no splitting of d-orbital. Even in the
degenerate d-orbitals, there is no vacant orbital. Thus, there is no absorption of visible light and
therefore, cuprous compounds are colourless.
(iii) Anhydrous copper sulphate (CuSO4) is also white. It is a d9 system but there are no ligands
and therefore no splitting of d-orbitals. One of the degenerate d-orbitals contains 9 electrons. But
there is no possibility of excitation of electrons and thus no absorption of energy. Hence CuSO4
anhydrous is white.
In general, we can say that a transition metal complex will be coloured if it possesses
incomplete d-orbitals. If there are no incomplete d-orbitals the complex will be colourless. Thus
complexes of Cu+ (d10), Zn2+ (d10), Ag+ (d10) and Ti4+ (d10) are colourless.
Limitations of Crystal Field Theory

The main limitations of crystal field theory are :
(i) It does not take into account the partial covalent character of metal-ligand bonds.
(ii) It does not explain the relative strengths of ligands. For example, it gives no explanation
as to why neutral water appears as a stronger ligand in electrochemical series than
negatively charged OH– ion.
(iii) It does not consider the multiple bonding ( bonds) between metal ion and the ligands.
Therefore, it does not explain the formation of  bonding in complexes.
(iv) It considers only d-orbitals of metal ions and does not consider at all the other metal
orbitals such as s, px, py, pz orbitals and the ligand  orbitals.
(v) It does not explain the charge transfer bands.

Comparison of Valence Bond Theory and Crystal Field Theory
The main points of comparison between valence bond theory and crystal field theory are given
below :
Crystal field theory Valence bond theory
1. The bond between metal ion and the 1. The bond between metal ion and the
ligand is taken as purely electrostatic. ligand is taken as purely covalent.
2. It helps to calculate the stabilization 2. The concept of crystal field stabilization
energies of complexes due to crystal energy does not exist here.
field splitting.
3. It takes into account the splitting of 3. It does not take into account the splitting
d-orbitals of the metal. of d-orbitals of metal.
4. It explains satisfactorily the colour of 4. It does not explain the colour of
complexes. complexes.
5. It does not consider the concept of 5. It considers the concept of hybridisation
hybridisation. of the orbitals of the metal ion before
complex formation.
6. It explains the effect of distortion in 6. It is unable to explain the distortion in
regular geometry of molecules (e.g. regular geometry of molecules.
tetragonal geometry).
7. It predicts theoretically the magnetic 7. It does not explain theoretically the
properties of complexes and predicts the number of unpaired electrons. It is unable
variation in magnetic moments with to predict the effect of temperature on the
temperature for complexes where  magnetic properties.
value is close to pairing energy.
SOLVED CONCEPTUAL PROBLEMS

Example 1. Calculate crystal field stabilization energies for the following :
(a) d 6 tetrahedral (b) d 4 tetrahedral
7
(c) d weak field octahedral (d) d 5 strong field octahedral
Solution. (a) d 6 tetrahedral
t2g
eg
Electronic configuration : e3 t23

CFSE = 3(– 6Dq) + 3(4Dq) = – 6 Dq
(b) d4 tetrahedral
t2
eg
Electronic configuration: eg2 t22

CFSE = 2(– 6Dq) + 2(4Dq) = – 4 Dq
(c) d7 weak field octahedral
eg
t2g
Electronic configuration : t2g5 eg2

CFSE = 5(– 4 Dq) + 2(6 Dq) = – 8 Dq
(d) d5 system strong field octahedral
eg
t2g
Electronic configuration : t2g5

CFSE = 5 × (– 4Dq) + 2P = – 20 Dq (Ignoring the pairing energy)
Example 2. Why does NH3 readily form complexes but NH4+ does not ? Explain.
Solution. NH3 contains a lone pair of electrons which coordinate with the metal ion to form
the complex compound. However, in NH4+ ion, the lone pair is bound to H+ and therefore, is not
available for bonding to metal ion. Therefore, NH4+ does not form complexes readily.
Example 3. Calculate CFSE for the following systems :
(i) d4 (high spin octahedral) (ii) d5 (tetrahedral)
(iii) d6 (low spin octahedral) (iv) d7 (high spin octahedral)
6
(v) d (tetrahedral)
Solution. (i) t2g3 eg1 : CFSE = – 6Dq (ii) e2 t23 : CFSE = 0
6
(iii) t2g : CFSE = – 24 Dq + 2P (iv) t2g5 eg2 : CFSE = – 8 Dq
(v) e3 t23 : CFSE = – 6 Dq
Example 4. Cu2+ ions are coloured and paramagnetic while Zn2+ ions are colourless and
diamagnetic. Explain.
Solution. The electronic configuration of Cu2+ and Zn2+ are as under:
Cu2+ : 3d9, Zn2+: 3d10
Cu2+ has one unpaired electron and therefore it is paramagnetic. On the other hand, Zn2+ has
no unpaired electrons and therefore it is diamagnetic.
In Cu2+, there is one vacancy in 3d orbitals to which an electron can be excited resulting in
d-d transition. Therefore, Cu2+ ions are coloured. In Zn2+, there is no possibility of excitation of
electrons because 3d orbitals are completely filled and hence are colourless.
Example 5. Show the d-electron configuration in the following complexes:
(i) [Co(NCS)4]2– tetrahedral
(ii) [Fe(CN)6]3– low spin octahedral.
Solution. (i) [Co(NCS)4]2–. In this complex ion Co is in +2 oxidation state and is d7 system.
Its electronic configuration is :
t23
e4
Electronic configuration : e4 t23
(ii) [Fe(CN)6]3–. In this complex ion, Fe is in +3 oxidation state and is d6 system. Its electronic
configuration is :
eg
t2g
Electronic configuration : t2g6 eg0

Example 6. Which of the following complexes has larger crystal field splitting of d-
orbitals in each pair ?
(i) [Co(H2O)6]2+ or [Co(H2O)6]3+ (ii) [Co(NH3)6]3+ or [Rh(NH3)6]3+
3–
(iii) [Co(CN)6] or [Co(NH3)6] 3+
Solution. (i) [Co(H2O)6]3+ (higher oxidation state of Co)

(ii) [Rh(NH3)6]3+ (element from 4d series)
(iii) [Co(CN)6]3– (strong ligand field of CN–)
Example 7. Draw the energy level diagram for [Pd(CN)4]2– square planar diamagnetic
complex showing the d-electron distribution.
Solution. Palladium in [Pd(CN)4]2– is in +2 oxidation state. It has d8 electronic configuration
as shown below:
dx2 – y2
dxy Electronic configuration:

(dxz)2 (dyz)2 (dz2)2 ( dxy)2
dz2
dxz dyz
Example 8. Predict which of the following statements are true or false:

(a) Crystal field splitting for tetrahedral field is always less than that for octahedral field.
(b) [CoCl4]2– is tetrahedral and diamagnetic.
(c) NO2– is weak field ligand as compared to NH3.
(d) Fe3+ octahedral weak field has 5 unpaired electrons.
Solution. (a) True (b) False
(c) False (d) True
Example 9. Draw crystal field splitting and calculate the number of unpaired electrons
in
(i) [Ni(CN)4]2– : square planner
(ii) [NiCl4]2– : tetrahedral
(iii) [Mn(CN)6]3– : octahedral
Solution. (i) Ni (II) : 3d8
dx2 – y2
sp (large)
dxy
dz2 No. of unpaired electrons = 0
dxz dyz
(ii) Ni (II) : 3d8 (iii) [Mn (CN)6]3–
Mn(III) : 3d 4
t2
eg
0 (large)
e t2g
No. of unpaired electrons = 2 No. of unpaired electrons = 2

Example 10. Cu (I) is diamagnetic whereas Cu (II) is paramagnetic.
Solution. Cu (II) has the outermost electronic configuration 3d9 and therefore, it has one
unpaired electron. Hence, it is paramagnetic. However, Cu (I) has the outermost electronic
configuration as 3d10. There is no unpaired electron and therefore, Cu (I) is diamagnetic.
Example 11. Calculate the number of unpaired electrons in the following :
(i) Cr3+ (octahedral strong field)
(ii) Co3+ (octahedral strong field)
(iii) Fe3+ (octahedral weak field)
Solution. (i) Cr3+ : Octahedral strong field
Cr3+ (d3) No. of unpaired electrons = 3
(ii) Co3+ : Octahedral strong field
Co3+ (d6) No. of unpaired electrons = 0
(iii) Fe3+ : Octahedral weak field
Fe3+ (d5) No. of unpaired electrons = 5
Example 12. Zn forms only Zn2+ and not Zn3+. Why?

Solution. In the formation of Zn2+, it acquires completely filled (3d10) configuration. It is a
stable configuration. Therefore, it is difficult to remove an electron from this filled 3d10 stable
configuration and hence Zn3+ is not formed.
EXERCISES
(Including Questions from Different University Papers)
Multiple Choice Questions (Select the correct answer)
1. Colour of a complex is satisfactorily explained by
(a) Werner’s theory (b) Valence bond theory
(c) Crystal field theory (d) ligand field theory
4
2. The CFSE for a high spin d octahedral complex ion is
(a) – 14 Dq (b) – 6 Dq
(c) – 12 Dq + P (d) zero
3. The largest crystal field splitting will be for the ligand (same metal ion)
(a) Ox2– (b) NO2–
(c) NH3 (d) CN–
4. Which of the following systems has maximum number of unpaired electrons ?
(a) d6 (tetrahedral) (b) d9 (octahedral)
7
(c) d (octahedral, high spin) (d) d4 (octahedral, low spin)
5. Which of the following complex ion would have the smallest crystal field splitting ?
(a) [Co(NH3)6]2+ (b) [Rh(NH3)6]3+
(c) [Ir(NH3)6]3+ (d) [Co(NH3)6]3+
6. The number of unpaired electrons in NiCl42– (tetrahedral) are
(a) two (b) zero
(c) one (d) four
7. Which of the following is a ligand which causes maximum crystal field splitting ?
(a) NH3 (b) F–
(c) CO (d) Ox2–
8. Which of the following has highest CFSE ?
(a) [TiF6]3– (b) [Mn(H2O)6]2+
(c) [FeCl4]2– (d) [Cr(H2O)6]3+
9. The order of splitting in cubic geometry is same as that in
(a) tetrahedral (b) square planar
(c) octahedral (d) tetragonally distorted octahedral
7
10. The number of unpaired electron in a d tetrahedral configuration is
(a) 3 (b) 2
(c) 1 (d) 7
11. Which of the following has no CFSE in octahedral field ?
(a) Fe3+ (high spin) (b) Co2+ (low spin)
(c) Fe3+ (low spin) (d) Cr3+ (high spin)
12. Choose the correct answer
(a) Copper sulphate hydroated solution is colourless
(b) Copper sulphate anhydrous in the solid form is white
(c) Copper sulphate hydrated in the solid form is white solution
(d) Cuprous sulphate solution is blue in colour
ANSWERS
1. (c) 2. (b) 3. (d) 4. (a) 5. (a) 6. (a)
7. (c) 8. (d) 9. (a) 10. (a) 11. (c) 12. (b)
Short Answer Questions

1. How will you account for the purple colour of [Ti(H2O)6]3+ ?
2. Give one example of an outer orbital complex.
3. Calculate CFSE for d4 high spin octahedral complex.
4. Draw energy level diagram showing splitting of five d-orbitals in octahedral field.
5. Calculate CFSE for d 9 tetrahedral complex.
6. Which complex has larger 0 value [Co(CN)6]3– or [Co(NH3)6]3+ ?
7. Which of the two [Co(H2O)6]2+ or [Co(H2O)6]3+ has smaller 0 value ?
8. What is the difference between low-spin and high-spin complexes ?
9. What is meant by spectrochemical series ?
10. What is meant by ligand ? Give five examples of ligand.
11. Define crystal field stabilization energy.
General Questions
1. (a) How do the d-orbital energy levels split when a transition metal ion is placed in an
octahedral crystal field of the ligands ?
(b) Explain the effect of nature of ligands and the geometry of the complex on the magnitude
of o.
2. (a) Explain how the orientation of d-orbitals in space leads to their splitting in a tetrahedral
field of ligands.
(b) Define CFSE and calculate its value for d 4 system in octahedral and tetrahedral fields.
(c) Explain with examples how the nature of ligands affects the magnitude of .
3. (a) What is the difference between inner orbital and outer orbital complexes ? Explain with
examples.
(b) Calculate the CFSE for the following system :
(i) d 4 (high spin octahedral) (ii) d 5 (tetrahedral)
(iii) d 6 (low spin octahedral)
(c) Explain briefly the splitting of d-orbitals in the case of a tetrahedral complex.
(d) Write short note on ferromagnetism and antiferromagnetism.
4. (a) What is crystal field splitting and crystal field stabilisation energy ? Discuss the structures
of [Co(NH3)6]3+ and [Cu(NH3)4]2+ ions on the basis of crystal field theory.
(b) Calculate CFSE for the following :
(i) d 4 high spin complex (Octahedral) (ii) d 5 strong field Octahedral
(iii) d 6 tetrahedral (iv) d 9 tetrahedral
5. (a) Give the salient features of crystal field theory.
(b) Discuss the crystal field splitting of d-orbitals in case of octahedral complexes.
(c) What is meant by spectrochemical series.
6. (a) Explain crystal field splitting in case of square planar examples.
(b) Calculate CFSE for the following systems :

(i) d 5 (low spin octahedral) (ii) d 6 (tetrahedral)
(iii) d 4 (high spin octahedral) (iv) d 7 (high spin octahedral)
(c) How will you account for the purple colour of [Ti(H2O)6]3+?
7. (a) Discuss the factors affecting the magnitude of crystal field splitting ().
(b) Define CFSE and calculate its value for the following systems.
(i) d 4 – high spin octahedral (ii) d 5 – tetrahedral
8. (a) What is crystal field splitting and what is crystal field stabilization energy ? Describe
the splitting of d-orbitals in octahedral and tetrahedral complexes.
(b) CuSO4 and Cu2SO4 lack colour but CuSO4.5H2O is blue. Explain.
9. (a) Define CFSE and calculate its value for d 5 system in octahedral and tetrahedral field.
(b) Explain crystal field splitting in square planar complexes.
(c) How will you account for the purple colour of [Ti(H2O)6]3+ ?
10. (a) Explain how the orientation of d-orbitals in space leads to the splitting in a tetrahedral
field of ligands.
(i) d 5 strong field Octahedral (ii) d 6 tetrahedral
7
(iii) d weak field octahedral (iv) d 4 tetrahedral
11. (a) Explain Crystal Field Splitting in tetrahedral complexes. Give reasons for smaller value
of crystal field splitting in tetrahedral than in octahedral complexes.
(b) How does Crystal Field Theory explain the magnetic character of coordinate complexes ?
Give the number of unpaired electrons in the following octahedral complexes :
(i) Ni (III) low spin (ii) Cr (III) low spin (iii) Ti (III) low spin.
12. (a) Define CFSE and calculate its value for d 4 system in octahedral and tetrahedral fields.
(b) How will you account for the purple colour of [Ti (H2O)6]3+ ?
13. (a) Give the salient features of crystal field theory.
(b) What is meant by spectrochemical series ? Explain.
(c) Explain the crystal field splitting in case of square planar complex.
14. (a) How does valence bond theory explain :
(i) [Ni (CN)4]2– is diamagnetic and square planar.
(ii) [Ni (CO)4] is diamagnetic and tetrahedral.
(b) Give the no. of unpaired electrons in octahedral strong field for :
(i) Cr3+ (ii) Co3+ (iii) Fe3+
(c) Why are salts of zinc, cadmium and mercury white ?
15. (a) Define crystal field splitting energy and discuss the crystal field splitting of d-orbitals
in case of octahedral complexes. Also calculate CFSE for d 5 (low spin Oh complex).
(b) Give reasons for the smaller value of crystal field splitting in tetrahedral than in
octahedral complexes.
(c) Discuss the bonding in [Fe(H2O)6]3+ and [Fe(CN)6]3– in terms of crystal field theory.
16. (a) Explain FeF63– is colourless whereas CoF63– is coloured.
(b) Write electronic configuration and calculate CFSE for d 4 (high spin octahedral).
(c) Calculate magnetic moment for the complex K4[Mn(CNS)6] (Spin only value).
17. Define crystal field stabilization energy. Calculate its value for d5 low and high spin
octahedral complexes.
18. (a) Explain crystal field splitting of d-orbitals in octahedral complexes.
(i) d 4 high spin (octahedral) (ii) d 5 strong field (octahedral)
(iii) d 6 tetrahedral (iv) d 9 tetrahedral
(c) Explain why the complex ion of transition metals are mostly coloured.
19. (a) What is meant by the terms
(i) crystal field splitting and
(ii) crystal field stabilization energy ? Briefly discuss the crystal field splitting in case
of square planar complexes.
(b) Describe the bonding in [FeF6]3– in terms of crystal field theory.
(c) Identify the complexes, from amongst the following, which has higher value of crystal
stabilisation :
(i) [Co(NH3)6]3+ and [CoF6]3– (ii) [Fe(CN)6]4– and [Fe(CN)6]3–
20. (a) Which of the two, [Co(NH3)6]3+ or [Ir(NH3)6]3+ has greater o value and why ?
21. (a) How do the d-orbitals energy levels split up of a transition metal ion when placed in
octahedral field of ligands ?
(b) Write electronic configuration and calculate CFSE for d 4 (high spin, oct) system.
22. (a) Give a brief account of limitations of valence bond theory in transition metal complexes.
(b) Find out the number of unpaired electrons in strong and weak octahedral complexes of
Co3+.
(c) Explain why is Ti3+ purple in aqueous solution, while Zn2+ is colourless ?
(d) Calculate the values of CFSE for the following systems :
(i) d 2 tetrahedral (ii) d 4 octahedral, high spin.
23. (a) How are magnitude of crystal field splitting in octahedral and tetrahedral complexes
related ?
(b) Calculate CFSE for d7 weak field & strong field (oct.).
(c) Discuss splitting of d-orbitals of metal atom or ion in octahedral field of ligands.
24. (a) Discuss the crystal field splitting in distorted octahedral complexes (Jahn-Teller effect).
(b) What is CFSE? Calculate CFSE for the following ions in octahedral field.
(i) d 4 strong field (ii) d 5 weak field
6
(iii) d weak field (iv) d 7 strong field
(c) What are inner and outer orbital complexes.
25. (a) Show diagrammatically the C.F. splitting of d-orbitals in square planar complexes and
write the d-electronic configuration of the following complexes :
(i) Sq. planar [Pd(CN)4]2– (ii) Sq. planar [Co(NCS)4]2–
(iii) Sq. planar [Pt(NH3)6]4+
(b) For the ligands CO, NH3, H2O and CN–, wirte their decreasing order of CF splitting with
Fe3+ ion.
(c) Explain on the basis of Valence Bond Theory, why :
(i) Ni (CO)4 is diamagnetic and tetrahedral
(ii) Tetrahedral complexes are generally high spin.
(d) Explain why octahedral complexes with d 4, d 5, d 6 and d 7 system form both types of
strong field and weak field complexes.
26. (a) Draw diagram showing splitting in square planar complexes.
(b) Using simple crystal field theory explain why [Mn(H2O)6]2+ is colourless.
(c) Calculate the crystal field stabilization energy for octahedral complexes of Fe3+ in a weak
field and also in strong field. Calculate the spin-only magnetic moment for these
complexes.
27. (a) Discuss the crystal field splitting of d-orbitals in case of tetrahedral complexes. Calculate
CFSE for d 3 (Td) and d 7 (Td).
(b) What is crystal field theory ? How does this theory account for the fact that [CoF6]3–
is paramagnetic but [Co(NH3)6]3+ is diamagnetic though both are octahedral ?
(c) CuSO4.5H2O is coloured compound while CuSO4 (anhydrous) is white. Explain on the
basis of CFT.
28. (a) Discuss the limitations of valence bond theory.
(b) Explain on the basis of CFT that [Ni(CN)6 ]2– is diamagnetic but [NiCl 4]2– is
paramagnetic.
(c) What are low and high spin complexes ?
29. (a) The magnetic moment of [Fe(H2O)6]3+ is 5.92 B.M. and that of [Fe(CN)6]3– is 1.73
B.M. Explain on the basis of CF theory.
(b) Why Ti3+ is purple in aqueous solution while Zn2+ is colourless.
(c) Explain why in tetrahedral complexes the subscript ‘g’ has been dropped from the orbital
notation.
(d) Give the salient features of crystal field theory.

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21

2.2. VALENCE BOND THEORY

Vacant hybrid Filled orbital M L

Fig. 2.1. Formation of a metal-ligand bond

3 sp2 Trigonal planar

4 dsp2 Square planar

5 dsp3 Trigonal bipyramidal

5 sp3d Square pyramidal

6 d2sp3 or sp3d2 Octahedral

Applications of valence bond theory

Complexes of Coordination Number 5

Fig. 2.5. Formation of [Fe(CN)6]3– complex involving d2sp3 hybridisation.

Fig. 2.6. Formation of [Fe(H2O)6]3+ complex involving sp3d2 hybridisation.

Complexes of coordination number 4

Fig. 2.8. Formation of tetrahedral [NiCl4]2– complex involving sp3 hybridisation.

Fig. 2.9. Formation of tetrahedral [Ni(CO)4] complex, xx represents

Limitations of valence bond theory

2.3. CRYSTAL FIELD THEORY (CFT)

Basic assumptions (features) of crystal field theory

Fig. 2.11. Shapes of five 3d orbitals.

Fig. 2.12. Representation of z2 orbital as a linear combination of d z 2  x 2 and d z 2  y 2 orbitals.

Crystal field Splitting in octahedral complexes (Coordination number 6)

dxy dyz dzX

Free ion Energy of orbitals in Splitting of orbitals

Fig. 2.15. Crystal field splitting in an octahedral complex.

Crystal Field Stabilization Energy (CFSE)

CFSE for various octahedral complexes

CFSE = 1(–4 Dq) = –4Dq

CFSE = 2(–4 Dq) = –8Dq

(iii) For a d3 system (e.g. Cr3+), the electronic configuration is t2g3.

CFSE = 3(–4 Dq) = –12Dq

CFSE = 3(– 4 Dq) + 1(6 Dq) = – 6 Dq.

CFSE = 5(– 4 Dq) + 2P

(b) Weak field :  o < P

CFSE = 3(– 4 Dq) + 2(6 Dq)

Number of Weak field CFSE Strong field CFSE

Crystal field splitting in tetrahedral complexes (Coordination number 4)

between X, Y and Z-axis (i.e. towards the

Fig. 2.17. Crystal field splitting in a tetrahedral field.

CFSE for tetrahedral complexes

CFSE = 1(– 6 Dq) = – 6Dq

(ii) For d2 system, the electronic configuration is e2.

CFSE = 2(– 6 Dq) = – 12Dq

CFSE = 2(– 6 Dq) + 1(4 Dq) = – 8Dq

d1 CFSE = – 6Dq d2 CFSE = – 12Dq

d3 CFSE = – 8Dq d4 CFSE = – 4Dq

d5 CFSE = 0 d6 CFSE = – 6Dq

d7 CFSE = – 12Dq d8 CFSE = – 8Dq

d9 CFSE = – 4Dq d 10 CFSE = 0

Crystal field splitting in tetragonal and square planar complexes

Fig. 2.20. Tetragonally distorted octahedron (a) elongation (b) flattening.

Crystal field theory and magnetic properties of complexes

High spin complex Low spin complex

Cobalt in [Co(NH3)6]3+ and [CoF6]3– is in +3 oxidation state and it has d6 configuration. It

1.4. FACTORS DETERMINING THE MAGNITUDE OF CRYSTAL

Weak field ligands

2. Oxidation state of the metal ion

3. Type of d-orbitals (transition series)

4. Geometry of the complex

2.5. COLOUR OF TRANSITION METAL COMPLEXES

3000 20000 10000

Fig. 2.22. Absorption spectrum of [Ti(H2O)6]3+.

6.023  1023  6.626  1034  3.0  108