28 A Textbook of Inorganic Chemistry - Volume I

•!• Bent Rule and Energetic of Hybridization

The success of valence-shell-electron-pair-repulsion (VSEPR) theory in rationalizing vanous
molecular geometries is quite remarkable as far as the simplicity is concerned. However, the failure ofVSEPR
theory in case of transition metal complexes or some other serious limitations like inert-pair effect in some
main group compounds are also undeniable facts which need to be addressed in a more sophisticated way. The
limited applicability of VSEPR theory is actually rooted in the fact that it does not consider any wave-
mechanical picture of atomic structure; in other words, as the VSEPR theory does not talk in terms of atomic
orbitals, it is quite bound in terms of flexibility required to model the chemical bonds. However, as we know
that the Lewis ideas of electron sharing inspired not the Sidgwick and Powell only, but some other physicist
like Walter Reitler and Fritz London also. Whilst on the one side the Sidgwick and Powell were working on
the VSEPR theory, which was completely immune to the concept of orbitals; Reitler and London were treating
the chemical bond in a hundred percent wave-mechanical framework. In 1926, Walter Reitler found out how
to use Schrodinger's wave equation to show that the single electron wave-functions of two hydrogen atoms
interact with each other to form a covalent bond. Soon after that, he and his associate Fritz London worked on
some more theoretical details of the theory and labelled it as valence bond theory (VBT). Thought the VBT
was quite effective in the calculation of bonding properties of the R z molecule, it was still unable to rationalize
complex molecules. Later, an American chemist, Linus Pauling modified the Reitler-London theory by
incorporating two key concepts, resonance (1928) and orbital hybridization (1930).

This document is an excerpt from the

book entitled "A Textbook of Inorganic
Chemistry - Volume 1 by Mandeep
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CHAPTER 1 Stereochemistry and Bonding in Main Group Compounds: 29

The initial development of the concept of orbital hybridisation was to explain the structure of simple
molecular geometries like CH4, BF3 or BeCb. The methane molecule had actually been the test case for all
bonding theories at that time. Before 1874, the CH4 molecule was thought be of square planar geometry with
carbon atom in the centre.

90°
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Figure 27. The visualization of structure of methane before 1874.

Now today it might seem very funny but at that time this structure was quite reasonable because it could explain
the observed magnetic moment which is zero for methane. The square planar structure has four C-H bonds of
equal length and all adjacent bonds at 90°; the cancellation of two opposite dipole moments from two trans
bonds would also give a zero dipole moment. However, if we attach four different groups to the carbon, the
resulting molecule is actually optically active i.e. it would rotate the plane of polarized light in left or light;
and therefore, must exist as two isomers (enantiomeric pair). It is possible only if the arrangement of groups
around central carbon is tetrahedral rather square planar; because the later one would exist as three isomers,
all optically inactive.

l-l"-. _,.,..-F
c
Cl __..- '-....Br

Two optical isomers of asymmetric carbon Three geometrical isomers of asymmetric C in sq uare-planar structure
All are optically inactive

Figure 28. Isomers for asymmetric carbon in tetrahedral and square-planar geometry.

A Dutch physical chemist, Jacobus Henricus van ' t Hoff, was the first to formulate the three-dimensional
carbon. In 1874, he showed that a tetrahedral arrangement of four different groups around a carbon atom is the
only way to give rise to two optical isomers. Using the same theory, he also explained the three isomers of
tartaric acid, one enantiomeric pair and one meso form. The tetrahedral coordination around carbon was also
proved in 1913 when X-ray diffraction studies of diamond showed a bond and angle of 109°28'.
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30 A Textbook of Inorganic Chemistry - Volume I

Now although the VSEPR theory, successor of Lewis idea (191 3), explained the tetrahedral
coordination in CH4 molecule by minimum repulsion of four bond pairs; it did not help us to understand the
nature of the orbitals involved in the bonding. Linus Pauling in 1931 Pauling pointed out that, in the frame of
simple "valence bond theory'', a carbon atom can form four bonds by using one s and three p orbitals by
promoting its one 2s electron to empty 2pz orbital and thus creating four half-filled orbitals. However, it might
would mean that a C atom creates three bonds at right angles (from use ofp subshell) and a fourth bond (weaker
one) using the s wave-function in some arbitrmy direction (this fourth C- H bond would be maximum away
from the other three bonds if it is put at 135°) as shown below.

Figure 29. The possible bonding mode in CH4 molecule from valence bond theory without considering
orbital hybridization (one lobe of p-orbitals in the right image are omitted for clarity.

The experimental results like four equal bonds separated by bond angle of 109.5° or the zero dipole
moment cannot be explained by the structure given above. Hence, the aforementioned geometry was a wrong
proposal for sure because, besides the bond angle anomaly, it would give rise to small dipole due to the
difference in electronegativity between C (2.5) and H (2.2). Moreover, according to simple valence bond
theory, as the bonding of hydrogen is happening with one sand three p orbitals of carbon, we should expect
one s- s bond to be shorter than three s- p bonds.
To explain this situation, Pauling thought that what would happen if instead of using pure ones and
three p wave functions, we use a linear combination of these fou r. Now though there can be infinite number of
linear combinations of these four single-electron-wave-functions, one should not forget that every single
electron-electron-wave-functions must be normalized and orthogonal to others. Linus Pauling found that out
of infinite linear combinations, there are only four expressions which are normalized as well as orthogonal to
each other. When he plotted these four linearly combined functions in space round carbon nucleus, they were
of same shape, same energy and were oriented at 109°28'. Linus Pauling created the tetrahedral frame of half-
filled orbitals, ready for overlap with approaching hydrogens. This was a revolutionmy step, he called these
functions as hybrid orbitals.
Hybridization is the intermixing of atomic orbitals of differen t energies and shapes so as to produce
new orbitals with same energy and equivalent shape.
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CHAPTER 1 Stereochemistry and Bonding in Main Group Compounds: 31

~ Characteristic Features ofHybridization

The orbital hybridization m mam group or the transition metal compounds has the following
characteristic features:
1. The number of hybrid orbitals is same as the number of atomic orbitals intermixed.

2. Hybrid orbitals are equivalent in shape and have same energies.

3. Hybrid orbitals form stronger bond than their pure atomic counterparts.

4. Hybrid orbitals are directed in specific direction and therefore control the geometry of molecule.
5. Only valence shell orbitals take part in hybridization.

6. There should be only small energy difference in the orbitals undergoing hybridization.
7. Electron promotion is not a necessary condition to be followed.

8. In addition to the half-filled orbitals, fully filled and empty orbitals can also undergo hybridization.
~ Types ofHybridisation
Hybrid orbitals are assumed to be the mixtures of atomic orbitals, superimposed on each other in
various proportions. For example, in the CH4 molecule, the hybrid orbital of C, which forms carbon- hydrogen
bond consists of 25% s-character and 75% p-character and is thus labelled as sp 3 hybridised. The main types
of hybridi zation are as follows.

1. sp-hybridization: Ones and one p-orbitals intermix to fo rm two hybrid orbitals oriented at 180° from each
other and form the basis for the linear geometry of BeCh, BeH2, BeF2 like molecules.

Be

Ground state 2s 2p

Be i
Excited state 2s 2p

Which gives

00<:)
180°
I
, 'I
Cl--Be--Cl
s Pz
Figure 30. Pictorial representation of sp-hybrid orbitals e.g. BeC)z molecule

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32 A Textbook of Inorganic Chemistry - Volume I

2. sp 2-hyb ridization : One s and two p -orbitals intermix to form three hybrid orbitals oriented at 120° from
each other and form the basis for the trigonal geometry of BF 3 type molecules .

B [!±] i
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Which gives

F
~ ·, 120°
/ B.Z,.
F F

Figure 3 1. Pictorial representation of sp 2 hybrid orbitals e.g. BF 3 molecule

3. sp3- hyb rid ization: Ones and three p -orbitals intermix to form four hybrid orbitals oriented at l 09°28 ' from
each other and form the basis for the tetrahedral geometry of Bf 3 type molecules.

c i i
Ground state 2s 2p

c i i i
Excited state 2s 2p

Which gives

H
J·:· 109°28'

H''\''' \ 'H
s Pz Py Px H

Figure 32. Pictorial representation of sp3 hy brid orbitals e.g. CH4 molecule

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CHAPTER 1 Stereochemistry and Bonding in Main Group Compounds: 33

4. sp3d-hybridization : One s, three p and one d-orbitals intermix to form five hybrid orbitals where three
hybrid orbitals are oriented at 120° and at 90 from two axial bonds to form the basis for the trigonal bipyramidal
geometry of PF s type molecules.

p i i i
Ground state 3s 3p 3d

p i i i i
Excited state 3s 3p 3d

Which gives

s Pz Py Px dz2
1-r,;:
9oc
:·

F
I ,,,,,,1 F
120"

Figure 33. Pictorial representation of sp3d hybrid orbitals e.g. PF 5 molecule.

5. sp3d2-hybridization: Ones, three p and two d-orbitals intermix to form five hybrid orbitals where three
hybrid orbitals are oriented at 120° and at 90 from two axial bonds to form the basis for the octahedral geometry
of SF6 type molecules.

s i i
Ground state 3s 3p 3d

s i i i i i
Excited state 3s 3p 3d

Which gives

F
L 90°
F,,,,,, I .. ,,,,, F
''"·s .I"' ·: 90°
F;"" I" 'F
F

F igure 34. Pictorial representation of sp 3d2 hybrid orbitals e.g. SF6 molecule.

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34 A Textbook of Inorganic Chemistry - Volume I

6. sp3d 3-hybridization: One s, three p and three d-orbitals intermix to form seven hybrid orbitals where five
equatorial hybrid orbitals are oriented at 72 ° from each other and at 90° from two axial hybrid robitals to form
the basis for the pentagonal bipyramidal geometry ofIF1 type molecules.

I i
Ground state 5s 5p 5d

I i i i i i i
Excited state 5s 5p 5d

Which gives

s Pz Py Px

Figure 35. Pictorial representation of sp 3d 3 hybrid orbitals e.g. IF1 molecule

>' Some Other Less Common Hybridization Schemes

Besides the simple and hyper-valent molecules like IF1, there are also some less common hybridization
schemes as given below.
1. dsp 2-hybridization: One d, two p and ones-orbitals intermix to form four hybrid orbitals which are oriented
at 90° to each other and form the basis for the square planar geometry of tetra-coordinated molecules.

Figure 36. The pictorial representation of dsp 2 orbitals hybridization scheme forming the basis for square
planar geometry.

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CHAPTER 1 Stereochemistry and Bonding in Main Group Compounds: 35

2. sp3d-hybridization: One s, three p and one d-orbitals intermix to form five hybrid orbitals which are
oriented at 90° to each other and form the basis for the square pyramidal geometry of penta-coordinated
molecules.

B,,,,,,,, I ,,\\\\\ B
'· ·A·~ '

s Pz Py d 2 2
B~ "B
Px x -y

Figure 3 7. The pictorial representation of sp3d hybrid orbitals forming the basis for square pyramidal
geometry.

3. sp3d2 -hybridization: One s, three p and two d-orbitals intermix to form six hybrid orbitals which are
oriented towards the comers of a trigonal prismatic geometry in hexa-coordinated molecules.

B B
~/
···A···
1

B'''/
B ' ' 'B 8
Figure 38. The pictorial representation of sp3d 2 orbitals hybridization scheme forming the for trigonal
prismatic geometry.

4. sp3d3-hybridization: Ones, three p and three d-orbitals intermix to form seven hybrid orbitals which are
oriented towards the comers of a mono-capped trigonal-prismatic geometry in hepta-coordinated molecules .

B~/B
,,.·A·.,,

B'/ I"""'' 'B

B B
B

Figure 39. The pictorial representation of sp3d3 orbitals hybridization scheme forming the for trigonal
prismatic geometry.

However, main group Compounds rarely show these hybridizations like dsp 2-square planar or sp 3d-
square pyramidal geometry due to stability issues which makes them more predictable structure than transition
metal complexes.
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36 A Textbook of Inorganic Chemistry - Volume I

~ Bent's Rule

The introduction of the concept of hybridisation by Linus Pauling was a huge success in the
rationalization of chemical bond, especially in the organic compounds. However, in the 1940s it became
apparent that a lot of molecular geometries, including even the simple ones, show slight deviations from the
predictions of orbital hybridization concept of valence bond theory. For instance, consider the case of H20
molecule; where the H-0-H bond angle is 104.5°, which far less than the normal tetrahedral angle of 109.5°.
Beside the isovalent species like H20 or NH3, the conventional hybridization theory was also unable to explain
why the Cl- C- CI and Me- C- Me bond angles in sp3-hybridized CChMe2 are 108.5° and 113°, respectively.

H
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104°30' H

Figure 40. The comparison of bond angle of methane and water though both have of sp 3 hybridization.

In 1947, a British chemist, A. D. Walsh tried to explain such inconsistencies by describing a correlation
between the electronegativity of ligand attached to carbon and the hybridisation scheme involved. it was
suggested that hybridisation may yield orbitals with different magnitude of s and p character. In 196 1, Henry
A. Bent published a more sophisticated treatment of the problem that correlated the molecular structure,
hybridisation scheme of the central atom atom, and the electronegativity strengths of attached groups. The
work is generally labelled as the Bent's rule, and is based upon the perturbation theory which suggests that
isovalent hybridization should transfer mores-character towards more electropositive substituents to maximize
the bonding energy. This can be explained in term of electron density available for bonding. The more
electropositive groups would be able to withdraw more electron density from p -orbital than s-orbital.
In the compounds containing mixed substituents and hybridised orbitals, a trend has been observed
according to which atomic s-character tends to concentrate in the orbitals that are directed towards
electropositive groups and atomic p -character tends to concentrate in the orbitals that are directed towards
electronegative groups.
Valence orbitals for main group elements consists of s and p orbitals with s-orbital having lower
energy, means the bonding orbital is lower in energy and shape more like s-orbital rather than p-orbital.
However, in case where the central atom or ion has lone pair, it will be having large s-character because s-
orbital are closer to the nucleus, allowing greater stabilization for the lone pair. The deviation of molecular
geometries from their perfectly tetrahedral, octahedral or other symmetrical counterparts can be explained and
predicted by examining the substituent groups and lone pair of electrons.
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 CHAPTER 1 Stereochemistry and Bonding in Main Group Compounds: 37

~ Applications ofBent's Rule

The Bent's rule can be used to rationalize many aspects of structure, bonding, spectra and the physical
and chemical properties of a wide range of compounds. Some of the important application of Bent's rule which
are quite popular in field of chemical science are given below.
1. Bond angles: i) In A(Cl)2(Me)2 molecules, where A is C , Si, Ge, Sn or Pb; the Cl- A- Cl bond angle is
smaller than that of Me- A- Me bond angle. With high electronegativity halogen substituent Cl, more p -
character is concentrated in A- C l bond than A- Me bonds. Subsequently, bonds with greater p-character have
smaller bond angles than those with s-character because s-orbitals are closer to the nucleus and hence exert
larger inter-electronic repulsion producing higher bond angles.

Cl Cl F
108°30' ,-I io1°20' .-1
~Si .,,,11
101 °40' --1

Cl
_).- c~''Me
M , Cl
/ ~Me
M
F/
j_Pb ..,,11
~Me
e , I
Me --:
-- e -.
113° 114°42' 134°48'

Figure 41 . Increasing p-character in A- X bond, decreasing halogen- A- halogen bond angle.

ii) In SF4, the bond angle of axial F- S- F bond is 173° (ideally 180°) and the equatorial F-S-F bond angle is
101 ° (ideally 120°). The axial as well as equatorial bond angles are decreased slightly due to increased s-
character of the Jone pair and more p-character in bond pairs. Furthermore, thionyl tetrafluoride shows the
same trend but slightly higher bond ang le between equatorial fluorines than that of sulfur tetrafluoride. This
anomaly can be explained in term of comparatively larger s-character in equatorial fluorines as the lone pair
has been replaced by more electronegative oxygen atom.

F F
/ 173° I 164°36'
\ ""'\\ F - '. ,11\\\F
S '-L_ 101 ° o===SQ 112°32'
\·' ~F \· ' ~F
F F
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iii) As one moves left to right in figure g iven, the substituents become more electronegati ve and the bond angle
between them decreases. According to Bent's rule, as the electronegativity strength of substituents increase,
orbitals rich in p-nature will be oriented towards those substituents. From the abovementioned argument, it
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38 A Textbook of Inorganic Chemistry - Volume I

will reduce the bond angle; which is in good agreement with the experimental data. If we compare this
justification w ith VSEPR theo1y, the VSEPR model cannot explain why the angle in dimethyl ether is larger
than normal tetrahedral angle of 109.5°. In the prediction of the bond angle in H20 molecule, the Bent' s rule
proposes that the hybrid orbitals which are rich in s-character should be oriented towards more electropositive
lone pairs, whilst the orbitals of more p -nature should point towards the hydrogens. This enhanced p -character
in orbitals decreases the corresponding bond angle to less than the normal tetrahedral of 109.5°. The same
reason can be applied to NH3 molecule, the other canonical cases of this kind.

,- --. 111°
,--,, 104°30' ,-- .. 103°32'
H3~,H3 I-I H
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Figure 43 . The decreasing trend of the B- A- B bond angle between substituents with increasi ng
electronegati vity.

2. Bond lengths: i) The bond lengths can also be changed by changing the hybridisation or by adding
electronegative groups to the central atoms. If a molecule geometry has X- A- Y component, replacement of
the group X by a more electronegative substituent would manipulate the hybridization of the central atom and
reduces the neighbouring A- Y bond length. Now owing to the higher electronegativity of fluorine than
hydrogen, the carbon of fluoromethane will direct its hybrid orbitals with higher s-character towards the three
H groups rather than the fluorine. In case of difluoromethane, only two hydrogens are present, so the s-
character in total is pointed towards them is less and more is pointed towards the two fluorine groups. This
reduces the carbon-fluorine bond lengths relative to fluoromethane molecule.

F F F F

H
~''H H~"F
H I-I H
~//p F F
~"F F
1.388 A 1.33 1 A 1.329 A 1.123 A
Figure 44. The decreasing trend of average carbon- fluorine bond lengths as we move from CH3F to CF4
molecular geometries.

This pattern continues to the Cf4 whose carbon-fluorine bonds have the largest s-character (25%) and the
shortest bonds in the whol e series.

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CHAPTER 1 Stereochemistry and Bonding in Main Group Compounds: 39

ii) The same pattern also continues for the chlorinated equivalents of CH4, though the effect is less efficient
because the chlorine is of lower electronegativity strength than the fluorine.

Cl Cl Cl Cl

H~H
I "11
H
~1 CI H H~Cl
I 11CI
Cl~CI
I 11 CI

1.783 A 1.772 A 1.767 A 1.766 A

Figure 45. Average carbon- chlorine bond length.

The abovementioned cases seem to prove that the atomic radius of chlorine is less significant than its
electronegativity strength because the prediction based on sterics factors alone would yield the opposite pattern
due to greater setting-apart tendency of larger chlorine groups. As the steric clarification is in contradiction
with the experimental results, Bent' s rule plays a significant role in structure elucidation.
iii) The simi lar trend is observed for single, double and triple carbon- carbon bonds, as the change of
hybridization scheme from sp3 to sp-type would lead to more s-character and therefore shorter bond.

R
R
\
c--cI
R
\ )-R R

\ - c== R

R~R ~R
R
..;f - C""-. R~R
RfJ R
R

1.54 A I.50 A I .46 A

Figure 46. Average carbon- carbon bond length.

3. JCH coupling constants: The Bent' s rule very much effective in explaining the variation of carbon-hydrogen
coupling constant with increasing electronegativity strength of the attached substituents. The 1H- 13C coupling
constants (Jrn) measured from nuclear magnetic resonance (NMR) spectra is one of the most direct scale that
can be used to estimate the magnitude of s character in a bonding overlap between carbon and hydrogen.
Now as we know from the quantum theory that the JcH values will be much greater in bonds with
more s character than the one with the less. Therefore, as the electronegative character of the attached group
increases, the magnitude of p character oriented towards the corresponding group increases as well. This
induces more s character in the bonds directed towards the methyl protons; which in turn, increases the Jrn
coupling constants.

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40 A Textbook of Inorganic Chemistry - Volume I

H OH F

H
~"H H
H~H
H
I ,,
H
~"H H

Jrn
(-CH 3 protons) 125 Hz 127 Hz 134 Hz 141 Hz 149 Hz

Figure 4 7. The variation of carbon-hydrogen coupling constants (Jrn) with increasing electronegative
strength of the attached group.

4. Inductive effect: One of the most important phenomena in the field of organic chemistry, the inductive
effect, can also be rationalized with the help of Bent's rule. The phenomenon of inductive effect is the actually
the passing of charge via the covalent bonds and Bent' s rule offers a reasonable mechanism for such
observations by exploiting the differences in hybridisation scheme involved. It has been observed that increase
in the electronegativity strength of the groups attached to the central carbon, the electron-withdrawing power
of the central carbon becomes also increases and can be measured by the polar-substituent-constant values.
According to the Bent's rule, the increase in the electronegativity of the groups attached would attract more p
character towards them; consequently, leaving higher s character for the C- R bond. Now because the s orbitals
have higher electron-density near the nuclei than their p counterparts, a shift of electron density towards the
carbon in the C- R bond is expected; which in tum would make the central carbon atom more electron-
withdrawing to the ligand attached i.e. R.

R R R R R

H3C
~1 CH3 u~"H Cl~''H ~'H ~"Cl
CH3 H H Cl Cl Cl Cl

Polar substituent
constant - 0.30 0.00 1.05 1.94 2.65

Figure 48. The variation polar-substituent-constants with increasing electronegative strength of the
attached group.

In words, we can say that the electron-withdrawing capability of the substituents-attached is transferred to the
neighbouring carbon atoms in the carbon chain under consideration. This is exactly the same conclusion what
the inductive effect states.

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CHAPTER 1 Stereochemistry and Bonding in Main Group Compounds: 41

~ Exceptions of Bent's Rule

The general statement of Bent's rule, atomic s-character concentrates in orbitals directed towards
electropositive substituents, is true only for main group compounds. However, transition metal complexes
show a quite strange behaviour. It has been observed that the group four transition metals Ti- Hf do not
rigorously follow Bent's rule. With these complexes, the more electronegative substituents have larger bond
angles indicating greater s-character. This can be explained by the fact that the d-orbitals in transition metals
are generally lower in energy than s-orbital. Thus, more electronegative substituents will be attracted to the
high lyings-orbitals. Transition metal orbitals are sd3 hybridized with very little contribution from p -orbitals.

,-, 106°12'
'

Figure 49. Distorted structure of TiMe2Cb.

The broad form of Bent' s rule can be stated as follows, "The energetically low-lying valence orbital
concentrates in bonds directed towards electropositive substituents". This satisfy both main group and
transition metal complexes.

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 International
Edition

A TEXTBOOK OF INORGANIC CHEMISTRY

Volume I
MANDEEP DALAL
Table of Contents
CHAPTER 1 .................................................................................................................................................. I I
Stereochemistry and Bonding in Main Group Compounds: ................................................................. 11
•!• VSEPR Theory ................................................................................................................................ 11

•!• dn-pn Bonds .................................................................................................................................... 23

•!• Bent Rule and Energetic of Hybridization ....................................................................................... 28

•!• Problems .......................................................................................................................................... 42

•!• Bibliography .................................................................................................................................... 43

CHAPTER 2 ...... ........................ ........................ .................................................................................... ........ 44

Metal-Ligand Equilibria in Solution: ...................................................................................................... 44
•!• Stepwise and Overall Formation Constants and Their Interactions ................................................ 44

•!• Trends in Stepwise Constants ................................................................................ ...... .................. .. 46

•!• Factors Affecting Stability of Metal Complexes with Reference to the Nature of Metal Ion and
Ligand ...................................................................................................................................................... 49

•!• Chelate Effect and Its Thermodynamic Origin ..... .. ...................... .. ...................... .. ......................... 56

•!• Determination of Binary Formation Constants by pH-metry and Spectrophotometry .................... 63

•!• Problems .......................................................................................................................................... 68

•!• Bibliography .................................................................................................................................... 69

CHAPTER 3 .............................................................................. ........................ ........................ .................... 70

Reaction Mechanism of Transition Metal Complexes-I: ....................................................................... 70
•!• Inert and Labile Complexes ...... ........................ .. ............................................................................. 70

•!• Mechanisms for Ligand Replacement Reactions ........ ........... .. ........... ........... .. ........... ............ ........ 77

•!• Formation of Complexes from Aqua Ions ....................................................................................... 82

•!• Ligand Displacement Reactions in Octahedral Complexes- Acid Hydrolysis, Base Hydrolysis .... 86

•!• Racemization of Tris Chelate Co1nplexes .............. ........... ............. ........... ............. ...... .. .......... .. ... .. 89

•!• Electrophilic Attack on Ligands ...................................................................................................... 92

•!• Problems .......................................................................................................................................... 94

•!• Bibliography ................................................. .... .. ................ .. .... .. ................... .. ... ............... ... ... ... ..... 95
CHAPTER 4 .................................................................................................................................................. 96

Reaction Mechanism of Transition Metal Complexes-II: ...................................................................... 96

•!• Mechanism of Ligand Displacement Reactions in Square Planar Complexes ................................ 96

•!• The Trans Effect .............................................................................................................................. 98

•!• Theories of Trans Effect ................................................................................................................ 103

•!• Mechanism of Electron Transfer Reactions - Types; Outer Sphere Electron Transfer Mechanism and
Inner Sphere Electron Transfer Mechanism .......................................................................................... 106

•!• Electron Exchange ......................................... ........................ ........................ ................................ 1 I7

•!• Problems ........................................................................................................................................ 121

•!• Bibliography .................................................................................................................................. 122

CHAPTER 5 ................................................................................................................................................ 123

Isopoly and Heteropoly Acids and Salts: ............................................................................................... 123

•!• Isopoly and Heteropoly Acids and Salts of Mo and W: Structures oflsopoly and Heteropoly Anions
......................................................................................................................................................... 123

•!• Problems ........................................................................................................................................ 152

•!• Bibliography .................................................................................................................................. 153

CHAPTER 6 ................................................................................................................................................ 154

Crystal Structures: .................................................................................................................................. 154

•!• Structures of Some Binary and Ternary Compounds Such as Fluorite, Antifluorite, Rutile, Antirutile,
Crystobalite, Layer Lattices - Cdb, Bih; Re0 3, Mn20 3, Corundum, Pervoskite, Ilmenite and Calcite.154

•!• Problems ........................................................................................................................................ 178

•!• Bibliography .................................................................................................. ........................ ........ 179

CHAPTER 7 ................................................................................................................................................ 180

Metal-Ligand Bonding: ........................................................................................................................... 180

•!• Limitation of Crystal Field Theory ................................................................................................ 180

•!• Molecular Orbital Theo1y - Octahedral, Tetrahedral or Square Planar Complexes ...................... 184

•!• n-Bonding and Molecular Orbital Theory ..................................................................................... 198

•!• Problems ........................................................................................................................................ 212

•!• Bibliography ........................................ ........................ ........................ .................. ... ..................... 2 I3

CHAPTER 8 ................................................................................................................................................ 214
Electronic Spectra of Transition Metal Complexes: ............................................................................ 214
•!• Spectroscopic Ground States ......................................................................................................... 214

•!• Correlation and Spin-Orbit Coupling in Free Ions for 1st Series of Transition Metals ................. 243

•!• Orgel and Tanabe-Sugano Diagrams for Transition Metal Complexes (d 1 - cf States) ................ 248
•!• Calculation of Dq, Band~ Parameters ......................................................................................... 280

•!• Effect of Distortion on the d-Orbital Energy Levels ..................................................................... 300

•!• Structural Evidence from Electronic Spectrum ............................................................................. 307

•!• Jahn.-Tella.r Effect .......................................................................................................................... 3 12

•!• Spectrochemical and Nephelauxetic Series ................................................................................... 324

•!• Charge Transfer Spectra ................................................................................................................ 328

•!• Electronic Spectra of Molecular Addition Compounds ................................................................. 336

•!• Pro.blems ........................................................................................................................................ 340

•!• Bibliography .................................................................................................................................. 341

CHAPTER 9 ................................................................................................................................................ 342

Magnetic Properties of Transition Metal Complexes: ......................................................................... 342
•!• Elementary Theory of Magneto-Chemistry ....................... ........................ .................................... 342

•!• Guoy's Method for Determination of Magnetic Susceptibility ..................................................... 35 1

•!• Calculation of Magnetic Moments ................................................................................................ 354

•!• Magnetic Properties of Free Ions ................................................................................................... 359

•!• Orbital Contribution: Effect of Ligand-Field ................................................................................ 362

•!• Application of Magneto-Chemistry in Structure Determination ................................................... 370

•!• Magnetic Exchange Coupling and Spin State Cross Over ............................................................ 375

•!• Problems ........................................................................................................................................ 384

•!• Bibliography .................................................................................................................................. 385

CHAPTER 10 ............................................................................................................................................... 386

Metal Clusters: ......................................................................................................................................... 386
•!• Structure and Bonding in Higher Boranes ..................................................................................... 386

•!• Wade's Rules ................................................................................................................................. 401

 •!• Carboranes .. ...................... .. ...................... .. ................. ........................ ........... .. .... .. ................ .. .... . 407

•!• Metal Carbonyl Clusters- Low Nuclearity Carbonyl Clusters .. ...... ...... ............ ...... ... ... ............ .. ... 412

•!• Total Electron Count (TEC) .......................................................................................................... 417

•!• Problems ........... ........................ ........................ ............................................................................. 424

•!• Bibliog·raphy .......... ........................................................................................................................ 425

CHAPTER 11 ............................................................................................................................................... 426

Metal-II Complexes: ................................................................................................................................ 426
•!• Metal Carbonyls: Structure and Bonding ......... ..... ........... ........ ..... ........... ........ ..... ... ..................... 426

•!• Vibrational Spectra of Metal Carbonyls for Bonding and Structure Elucidation .......................... 439
•!• Important Reactions of Metal Carbonyls ....................................................................................... 446

•!• Preparation, Bonding, Structure and Important Reactions of Transition Metal Nitrosyl, Dinitrogen
and Di oxygen Complexes ..................................................................................................... ................. 450

•!• Tertiary Phosphine as Ligand ........................................................................................................ 463

•!• Problems ....... .. .. .... ............ .... .. .. .... ............ .... .. .. .... ...... .. ...... .. .... .... ...... .. ... ...... .. ... .. ...... ..... ...... .. ... .. . 469

•!• Bibliography .................................................. ........................ ........................... ...... ...... ............ ..... 4 70

INDEX .......................................................................................................................................................... 471
 Mandeep Dalal is an Indian research scholar wha
is primarily working in the field af Science and
Philosophy. He received his Ph.D in Chemistry
from Maharshi Dayanand University. Rahtak. in
20!8. He is also the Founder and Director af
"Dalal Institute". a nan-profit private educational
organization in India which is trying ta
revolutionize the made af higher educ:atian in
Chemistry. He has published mare than 25
research papers in various international
Mandeep Dalal scientific journals. inc:luding mostly fram Elsevier
(M.Sc, Ph.D, CSIR UGC - NET JRF, IIT - GATE)
(LISA) and Springer (Europe).
Founder & Director, Dalal Institute
Contact No: +91-9802825820
Homepage: www.mandeepdalal.com
E-Mail: [email protected]

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