Beruflich Dokumente
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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.
M L M L
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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
4 sp3 Tetrahedral
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METAL LIGAND BONDING IN TRANSITION METAL COMPLEXES 27
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.
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28 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
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.
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METAL LIGAND BONDING IN TRANSITION METAL COMPLEXES 29
Configuration of
3d 4s 4p
Fe
Fe (III)
d2sp3 Hybridisation
[Fe(CN)6]3–
3d 4s 4p
Fe
Fe (III)
sp3d2 Hybridisation
[Fe(H2O)6]3+
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30 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
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–
Ni
Ni (0)
sp3 Hybridisation
[Ni(CO)4]
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METAL LIGAND BONDING IN TRANSITION METAL COMPLEXES 31
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.
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32 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
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.
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METAL LIGAND BONDING IN TRANSITION METAL COMPLEXES 33
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
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34 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
z z z
+ + y +
–
– – x + x x
–
+ + y +
dz2 – x2 dz2 – y2 dz2
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.
X X
Y
dz2 dx2 – y2
eg– orbitals
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METAL LIGAND BONDING IN TRANSITION METAL COMPLEXES 35
Z Z Z
X X X
Y Y Y
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
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36 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
(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.
(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.
(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
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METAL LIGAND BONDING IN TRANSITION METAL COMPLEXES 37
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
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.
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38 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
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)
The systems d1, d2, d3, d9 and d10 have same configuration in weak field and strong field and,
therefore, have same CFSE values.
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METAL LIGAND BONDING IN TRANSITION METAL COMPLEXES 39
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
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40 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
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
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METAL LIGAND BONDING IN TRANSITION METAL COMPLEXES 41
(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.
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.
Precisely, the pairing energy values should also be taken into consideration. However, to
simplify the matter, these have been omitted here.
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42 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
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.
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METAL LIGAND BONDING IN TRANSITION METAL COMPLEXES 43
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
eg
eg
0 Large0 value
0 Small0 value
t2g
3– 3+
[CoF6] [Co(NH3)6]
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44 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
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
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METAL LIGAND BONDING IN TRANSITION METAL COMPLEXES 45
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.
The ligands are arranged in increasing order of crystal field splitting as given below. This
regular order is called spectrochemical series.
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46 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
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METAL LIGAND BONDING IN TRANSITION METAL COMPLEXES 47
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48 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
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.
eg
t2g
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METAL LIGAND BONDING IN TRANSITION METAL COMPLEXES 49
t2g
eg
t2
eg
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50 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
eg
t2g
eg
t2g
t23
e4
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METAL LIGAND BONDING IN TRANSITION METAL COMPLEXES 51
(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
dx2 – y2
dxz dyz
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52 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
dx2 – y2
sp (large)
dxy
dxz dyz
Mn(III) : 3d 4
t2
eg
0 (large)
e t2g
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METAL LIGAND BONDING IN TRANSITION METAL COMPLEXES 53
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
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54 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
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)
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.
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METAL LIGAND BONDING IN TRANSITION METAL COMPLEXES 55
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56 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
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.
(b) Calculate CFSE for the following :
(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.
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METAL LIGAND BONDING IN TRANSITION METAL COMPLEXES 57
(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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