Unit 3

Chemical bonding

1
 CHEMICAL BONDNG
• Properties of substances are (in part)
determined by chemical bonds.
• Strong attractive forces that hold atoms
and ions together in compounds/molecules.
• Ionic bond: Involves transfer of one or
more electrons from the valence shell
• A positive and negative ion form giving rise
to electrostatic forces between atoms
forming the bond.
• Occurs between elements with low
ionization energy and high electron affinity.
2
 CHEMICAL BONDNG

K([Ar]4s1) + Cl([Ne]3s23p5) → K+([Ar]) +

Cl([Ar])

3
Humorous chemist – Ionic bonding

4
 Chemical bonding
• Covalent bond: One or more electrons are
shared between two atoms.
• Coordinate covalent bonds: The shared
electron comes from the lone pair of one
of the atoms in the molecule.
• Transfer of electrons results in the more
stable configurations in the ions.
• The tendency to form this stable
configuration is known as octet rule.
Exception He configuration.
5
 Chemical bonding
• Why a chemical bond is formed?
• formed by an atom to get more stability.
• Every atom tries to get more stability by
lowering its potential energy.
• This can be achieved by making a bond.
• The potential energy decreases when two
atoms attract each other.
• Hence energy is liberated during the
formation of a chemical bond i.e., it is an
exothermic process.
 Chemical bonding
• Few fundamental questions:
• What is the connection between stability
and electronic configuration?
• The noble gas atoms with octet configuration
in their outer shells are very stable.
• Hence every atom tries to get octet
configuration either by losing or gaining or
sharing electrons.
• This is also called as octet rule.
• However this rule may not be followed always
by the atoms.
 1. Ionic bond

• The electrostatic force of attraction

between two oppositely charged ions is
called ionic bond.
 An ionic bond is formed due to transfer
of electrons from one atom to another.
 The atom that loses electrons will form
a cation and the atom that gains
electrons will form an anion.
The formation of ionic bond between
two atoms can be visualized as follows:
 2. Covalent bond
• The chemical bond formed between two
atoms due to the sharing of electron pair(s)
is called covalent bond.
 It is formed between two atoms for
which the electronegativity difference
is less than 1.7 on Pauling's scale.
 Usually two nonmetal atoms form a
covalent bond.

• E.g. H2, F2, HCl, H2O etc.

2. Covalent bond
Lewis Symbols and Lewis Structure

• A Lewis structure (or Lewis dot symbols) is

a chemical symbol of an element surrounded
by dots, each representing one of the s
and/or p valence electrons of the atom.
• Lewis symbol is used to represent the
distribution of valence electrons in an atom
or molecule.
12
Lewis Symbols and Lewis Structure

Li Na F
F F F F
bonding
Fate of valence Non-bonding
electrons
electrons
electrons in
covalent bonds. F F

13
 Lewis Theory
1. Electrons in the outermost Double bonds
electronic shell, play a
fundamental role in chemical O C O
bonding
2. In some cases, electrons are
O C O
transferred resulting in positive
and negative ions, attract each
other, form ionic bonds Triple bonds
3. In other cases one more pairs of N N
electrons are shared between
atoms to form a covalent bonds N N
4. Electrons are transferred in such
a way that each atom attains a
stable electron configuration 14
 Writing Lewis Structures - Steps
1. Determine the total number of valence
electrons in the structure.
2. Identify the central atoms - often the atom
with the lowest electronegativity. Hydrogen,
is never a central atom.
3. Write the skeletal structure, and join the
atoms in the structure by single covalent
bonds.
4. For each single bond thus formed, subtract
two from the total number of the valence
electrons
15
 Writing Lewis Structures - Steps
5. With the remaining valence electrons,
complete the octets of the terminal atoms.
Then to the extents possible, complete the
octets of the central atom (s)
6. If at this stage, the central atom (s) lacks
an octet, form multiple covalent bonds by
converting lone pair electrons from
terminal atoms into bond pairs.

16
 Example problem
 Construct Lewis structures for the
molecule H2O.

 Solution

 Step 1
Total number valence electrons:
1+1+6=8
17
 Example problem
 Step 2, 3
Identify central atom, use pair of
electron per bond e.g.

O―H single bonds, H―O―H

 Step 4
Distribute remaining electrons around
atoms to obtain noble gas configuration.
18
 Formal charge helps select correct
Lewis structures
• Guideline to determination of the Lewis
structure when competing structures are
available.
• An arbitrarily-calculated quantity known as
the formal charge can often serve as a guide.
• It is the electric charge as atom would
have if all bonding electrons were shared
equally with its bonded neighbors.
• The Lewis structure of the molecule with
no formal charge is the preferred one.
19
 Formal charge helps select correct
Lewis structures
• The formal charge must be as small as
possible
• Negative charges usually appear on the most
electronegative atoms, positive on the least
electronegative atoms
• The sum of the formal charges of the atoms
in the Lewis structure must equal to zero for
a neutral atom or equal to the ionic charge
for a polyatomic ion
20
 Formal charge helps select correct
Lewis structures
Calculation

No. valence No. unshared

No. bonds
FC = electrons in  
to atom electrons
isolated atom

21
 Calculation of formal charge
Example

Find the formal charges of all the atoms in

the sulphuric acid structure.
O

H O S O H

O
22
 Calculation of formal charge

There four bonds to the S atom

Formal charge on S = 6 – (4 + 0) = + 2
An isolated S atom has There are no. unshared
6 electrons pairs on the S

Sulfur: FC = 6 – (4 + 0) = +2
Hydrogen: FC = 1 – (1 + 0) = 0
Hydroxyl oxygen: FC = 6 – (2 + 4) = 0
Oxygen not bonded to hydrogen: FC = 6 – (1 + 6) = –1
23
Both seem correct..but only
one is
Draw the Lewis structure of iodomethane,
CH3I
 Carbon dioxide molecule (CO2):

 Note: The C=O bond is polar due to

electronegativity difference between
carbon (e.n. = 2.1) and oxygen (e.n. = 3.5) is
1.4.
• Question to ponder: What is the overall
polarity of the carbon dioxide molecule? Is
it polar or non polar?
 Too many structures – resonance hybrids
• Sometimes a single structure fails to explain
experimental measurements: bonds lengths and
energies.
• The concept of resonance is used to indicate a
composite or “average” structure. Two or more
structures are possible.

There is no true
double bond
27
 Exception to the octet rule

• Boron tends to form compounds in which the boron

atom has fewer than eight electrons around it (it
does not have a complete octet).
BH3 = 6e–

H
H B H

Copyright © Cengage Learning. All rights reserved 28

 Exception to the octet rule

• When it is necessary to exceed the octet rule for one of

several third-row (or higher) elements, place the extra
electrons on the central atom.
SF4 = 34e– AsBr5 = 40e–
F Br Br
F S F Br As Br
F Br

Copyright © Cengage Learning. All rights reserved 29

 Exception to the octet rule
CONCEPT CHECK!
Draw a Lewis structure for each of the following
molecules:

BF3
PCl5
SF6

Copyright © Cengage Learning. All rights reserved 30

 Exception to the octet rule
Let’s Review
• C, N, O, and F should always be assumed to
obey the octet rule.
• B and Be often have fewer than 8 electrons
around them in their compounds.
• Second-row elements never exceed the octet
rule.
• Third-row and heavier elements often satisfy
the octet rule but can exceed the octet rule by
using their empty valence d orbitals.
Copyright © Cengage Learning. All rights reserved 31
 Exception to the octet rule
Let’s Review

• When writing the Lewis structure for a

molecule, satisfy the octet rule for the
atoms first.
• If electrons remain after the octet rule
has been satisfied, then place them on the
elements having available d orbitals
(elements in Period 3 or beyond).

Copyright © Cengage Learning. All rights reserved 32

VALENCE SHELL ELECTRON PAIR
REPULSION (VSEPR) THEORY
 The Valence-Shell Electron-Pair
Repulsion Theory (VSEPR) [pronounced
vesper]
• Shapes of molecules are determined by
experiment or quantum mechanical
calculations
• VSEPR theory uses Lewis structures to
predict the molecular geometry of
covalently bonded molecules.
• Focuses on pairs of electrons in the
valence shell. Electrons repel each other in
a bond or unshared. 34
 VSEPR
• It states that the 3-dimensional arrangement
of atoms surrounding a central atom is
determine by:
1. Repulsions between the bonding and the
non-bonding electron pairs in the valence
shell of the central atom.
2.These electrons arrange themselves as far
apart as possible, minimizing repulsion.
3.Double bonds and triple bonds can be
treated as single bonds between
neighbouring atoms. 35
The basic ideas of the theory are:

1) The electron pairs in the valence shell

around the central atom of a molecule
repel each other & tend to orient in
space so as to minimize the repulsions &
maximize the distance between them.
2) There are two types of valence shell
electron pairs viz.,
i) Bond pairs &
ii) Lone pairs
 The basic ideas of the theory
3) The order of repulsion between different
types of electron pairs is as follows:

Lone pair-Lone pair > Lone Pair-Bond

pair > Bond pair-Bond pair

Note:
 The bond pairs are usually represented by
a solid line, whereas the lone pairs are
represented by a lobe with two electrons.
 The basic ideas of the theory
4) The shape of a molecule can be predicted
from the number and type of valence shell
electron pairs around the central atom.

 When the valence shell of central atom

contains only bond pairs,..
… the molecule assumes symmetrical
geometry due to even repulsions
between them.
 The basic ideas of the theory
 However the symmetry is distorted when
there are also lone pairs along with bond
pairs due to uneven repulsion forces.
 The best spatial arrangement of the
bonding pairs of electrons in the valence
orbitals is one in which the repulsions are
minimized.
Valence shell electron pair repulsion (VSEPR) model:

Predict the geometry of the molecule from the electrostatic

repulsions between the electron (bonding and nonbonding) pairs.

# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

AB2 2 0 linear linear

B B

10.1
 0 lone pairs on central atom

Cl Be Cl

2 atoms bonded to central atom 10.1

 VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

AB2 2 0 linear linear

trigonal trigonal
AB3 3 0
planar planar

10.1
10.1
 VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

AB2 2 0 linear linear

trigonal trigonal
AB3 3 0
planar planar
AB4 4 0 tetrahedral tetrahedral

10.1
10.1
 VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

AB2 2 0 linear linear

trigonal trigonal
AB3 3 0
planar planar
AB4 4 0 tetrahedral tetrahedral
trigonal trigonal
AB5 5 0
bipyramidal bipyramidal

10.1
10.1
 VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

AB2 2 0 linear linear

trigonal trigonal
AB3 3 0
planar planar
AB4 4 0 tetrahedral tetrahedral
trigonal trigonal
AB5 5 0
bipyramidal bipyramidal
AB6 6 0 octahedral octahedral

10.1
10.1
lone-pair vs. lone pair lone-pair vs. bonding bonding-pair vs. bonding
repulsion
> pair repulsion
> pair repulsion
 VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

trigonal trigonal
AB3 3 0
planar planar
trigonal
AB2E 2 1 bent
planar

10.1
 VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

AB4 4 0 tetrahedral tetrahedral

trigonal
AB3E 3 1 tetrahedral
pyramidal

10.1
 VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

AB4 4 0 tetrahedral tetrahedral

trigonal
AB3E 3 1 tetrahedral
pyramidal

AB2E2 2 2 tetrahedral bent

O
H H

10.1
 VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry
trigonal trigonal
AB5 5 0
bipyramidal bipyramidal
trigonal distorted
AB4E 4 1
bipyramidal tetrahedron

(see-saw)

10.1
 VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry
trigonal trigonal
AB5 5 0
bipyramidal bipyramidal
trigonal distorted
AB4E 4 1
bipyramidal tetrahedron
trigonal
AB3E2 3 2 T-shaped
bipyramidal
F

F Cl

10.1
 VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry
trigonal trigonal
AB5 5 0
bipyramidal bipyramidal
trigonal distorted
AB4E 4 1
bipyramidal tetrahedron
trigonal
AB3E2 3 2 T-shaped
bipyramidal
trigonal
AB2E3 2 3 linear
bipyramidal
I

I 10.1
 VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

AB6 6 0 octahedral octahedral

octahedral square
AB5E 5 1
pyramidal
F
F F
Br
F F

10.1
 VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

AB6 6 0 octahedral octahedral

octahedral square
AB5E 5 1
pyramidal
octahedral square
AB4E2 4 2
planar
F F
Xe
F F

10.1
 Polar Covalent Bond

• Unequal sharing of electrons between

atoms in a molecule.
• Results in a charge separation in the bond
(partial positive and partial negative
charge).

59
The Effect of an Electric Field on
Hydrogen Fluoride Molecules
 or  indicates a positive or negative fractional charge.

Copyright © Cengage Learning. All rights reserved 60

 Electronegativity

• The ability of an atom in a molecule to

attract shared electrons to itself.
• For a molecule HX, the relative
electronegativities of the H and X atoms
are determined by comparing the measured
H–X bond energy with the “expected” H–X
bond energy.

Copyright © Cengage Learning. All rights reserved 61

 Electronegativity

• On the periodic table, electronegativity

generally increases across a period and
decreases down a group.
• The range of electronegativity values is
from 4.0 for fluorine (the most
electronegative) to 0.7 for cesium (the
least electronegative).

62
The Pauling Electronegativity Values

Copyright © Cengage Learning. All rights reserved 63

CONCEPT CHECK!

If lithium and fluorine react, which has more attraction

for an electron? Why?

In a bond between fluorine and iodine, which has

more attraction for an electron? Why?

Copyright © Cengage Learning. All rights reserved 64

CONCEPT CHECK!
What is the general trend for electronegativity
across rows and down columns on the periodic
table?

Explain the trend.

Copyright © Cengage Learning. All rights reserved 65

 Electronegativity

Copyright © Cengage Learning. All rights reserved

 EXERCISE!

Arrange the following bonds from most to least polar:

a) N–F O–F C–F

b) C–F N–O Si–F
c) Cl–Cl B–Cl S–Cl
a) C–F, N–F, O–F
b) Si–F, C–F, N–O
c) B–Cl, S–Cl, Cl–Cl

Copyright © Cengage Learning. All rights reserved 67

CONCEPT CHECK!

Which of the following bonds would be the least

polar yet still be considered polar covalent?

Mg–O C–O O–O Si–O N–O

Copyright © Cengage Learning. All rights reserved 68

CONCEPT CHECK!

Which of the following bonds would be the most

polar without being considered ionic?

Mg–O C–O O–O Si–O N–O

Copyright © Cengage Learning. All rights reserved 69

 Dipole Moment
• Property of a molecule whose charge
distribution can be represented by a center
of positive charge and a center of negative
charge.
• Use an arrow to represent a dipole moment.
– Point to the negative charge center with
the tail of the arrow indicating the
positive center of charge.
Copyright © Cengage Learning. All rights reserved 70
Dipole Moment

71
No Net Dipole Moment (Dipoles
Cancel)

Copyright © Cengage Learning. All rights reserved 72

Dipole Moments and Polar Molecules

electron rich
electron poor
region
region

H F

d+ d-

m=Qxr
Q is the charge
r is the distance between charges
1 D = 3.36 x 10-30 C m 10.2
10.2
10.2
 Which of the following molecules have a dipole moment?
H2O, CO2, SO2, and CH4

O S O
H
H O
dipole moment dipole moment
polar molecule polar molecule

H C H
O C O

no dipole moment H
nonpolar molecule no dipole moment
nonpolar molecule
10.2
Does BF3 have a
dipole moment?

10.2
Does CH2Cl2 have
a dipole moment?

10.2
10.2
• No bonds reach 100% ionic character even with
compounds that have the maximum possible
electronegativity difference.

 measured dipole moment of X  Y 

% ionic character of a bond =   100%
 calculated dipole moment of X+Y  
 

Copyright © Cengage Learning. All rights reserved 80

The relationship between the ionic character of a covalent bond
and the electronegativity difference of the bonded atoms

Copyright © Cengage Learning. All rights reserved 81

 Concept of hybridisation
• Orbital hybridisation (or hybridization) is
the concept of mixing atomic orbitals into
new hybrid orbitals (with different
energies, shapes, etc., than the component
atomic orbitals) suitable for the pairing of
electrons to form chemical bonds in
valence bond theory.

82
 Concept of hybridisation
• For example, in a carbon atom which forms
four single bonds the valence-shell s orbital
combines with three valence-shell p orbitals
to form four equivalent sp3 mixtures which
are arranged in a tetrahedral arrangement
around the carbon to bond to four
different atoms.

83
 Concept of hybridisation
• Hybrid orbitals are useful in the
explanation of molecular geometry and
atomic bonding properties and are
symmetrically disposed in space.
• Usually hybrid orbitals are formed by
mixing atomic orbitals of comparable
energies.

84
sp3 hybridization (4 hybrid orbitals)

• Methane CH4, Ethane, C2H6

• The ground state of C reveals a pair of
electrons in the 2s and two single electrons
in the 2p.
• This is not consistent with the need for four
single electrons required to form the four
bonds with the hydrogens, ..
• …so again, electrons are promoted into the p
subshell just prior to bonding.
sp3 hybridization (4 hybrid orbitals)
 Types of hybridisation
sp3

A set of four equivalent orbitals can be obtained that are linear combinations of the valence-
shell (core orbitals are almost never involved in bonding) s and p wave

87
Mixing of orbitals

88
Relative energies of pure and hybrid orbitals

89
90
sp2

91
Orbital overlaps in sp2 hybridisation

92
sp

93
Orbital overlaps in sp hybridisation

94
95
Based on the nature of the mixing orbitals,
the hybridization can be classified as,

• sp hybridization (beryllium chloride,

acetylene)
• sp2 hybridization (boron trichloride,
ethylene)
• sp3 hybridization (methane, ethane)
• sp3d hybridization (phosphorus
pentachloride)
• sp3d2 hybridization (sulphur hexafluoride)
• sp3d3 hybridization (iodine heptafluoride)96
Hybridisation and molecule shape

97
Hybridisation and molecule shape

98
 Valence Bond Theory
• Valence bond theory states that overlap
between two atomic orbitals forms a covalent
bond between two atoms.
• Two atoms that have unpaired electrons in
their orbitals can overlap to give rise to a
chemical bond.
• A sigma bond (σ) forms when two atomic
orbitals overlap between the nuclei of two
atoms (also known as the internuclear axis).
99
 Valence Bond Theory
• Pi bonds (π) occur when two atomic orbitals
overlap outside of the space between the
nuclei (outside of the internuclear axis).
• The electrons in the overlapping orbitals get
paired & confined between the nuclei of two
atoms.

100
 Valence Bond Theory
• The electron density between two bonded
atoms increases due to overlapping.
• This confers stability to the molecule.
• The greater the extent of overlapping,
stronger is the bond formed.
• The direction of the covalent bond is along
the region of overlapping of the atomic
orbitals i.e., covalent bond is directional.
 Valence Bond Theory
• There are two types of covalent bonds
based on the pattern of overlapping as
follows:
1) σ-bond:
 The covalent bond formed due to
overlapping of atomic orbital along
the inter nucleus axis is called σ-
bond.
 Valence Bond Theory
This head-on overlap of orbitals is
referred to as a sigma bond (σ).

 It is a stronger bond and cylindrically

symmetrical.
 Depending on the types of orbitals
overlapping, the σ-bond is divided into
following types:
 Covalent Bond
• The covalent bond is the electrostatic
attraction between the two nuclei of the
bonded atoms and the pair of electrons
shared between them.
• The atomic orbitals involved can be any of
those found in the atoms, but we shall limit
our discussion to those involving only s and p
orbitals
• There are four ways in which the s and the p
orbitals can overlap to form a covalent bond
Types of overlaps in covalent bond
1. End on overlap of two s orbital or two p
orbitals (sigma bond)
 Types of overlaps in covalent bond

2. Sideways overlapping of two p orbitals

(π bond)
 Types of overlaps in covalent bond
• An end-on overlap leads to the formation
of sigma (σ) bonds.
• This leads to the formation of a single
covalent bond between the two atoms.
• A sideways overlap of two p orbital leads
to the formation of a pi (π) bond.
• A feature of a π bond is that it cannot
form until a ‘σ’ bond has been formed.
 Types of overlaps in covalent bond
• For this reason π bond only exist between
atoms that are joined by double or triple
bonds
• The different types of orbital overlap are
shown in the following examples.
• There is a fourth way that overlap can
occur.
• An s and p orbital can overlap end on.
 Types of overlaps in covalent
bond

• This overlap, however, can only result

from atoms of two different elements.
• This almost always leads to the formation
of a variant of a covalent bond, known as
a polar covalent bond.
Summary of Overlap of Orbitals

110
The VBT
 Bonding in BF3

For boron to bond with three fluoride atoms in boron trifluoride

(BF3), the atomic s- and p- orbitals in boron’s outer shell mix to
form three equivalent sp2 hybrid orbitals. Boron trifluoride (BF3)
has a boron atom with three outer-shell electrons in its normal or
ground state, as well as three fluorine atoms, each with seven
outer electrons. One of the three boron electrons is unpaired in
the ground state. In order to explain the bonding, the 2s orbital
and two of the 2p orbitals (called sp2 hybrids) hybridize; one
empty p-orbital remains.

112
113
Geometry of BF3

114
Bonding in Methane

115
116
 Molecular Orbital Theory
• In molecular orbital theory, electrons in a molecule are not
assigned to individual chemical bonds between atoms, but are
treated as moving under the influence of the atomic nuclei in
the whole molecule.
• Molecular orbital (MO) theory uses a linear combination of atomic orbitals
(LCAO) to represent molecular orbitals resulting from bonds between
atoms. These are often divided into three types, bonding and antibonding,
A bonding orbital concentrates electron density in the region between a
given pair of atoms, so that its electron density will tend to attract each of
the two nuclei toward the other and hold the two atoms together. An anti-
bonding orbital concentrates electron density "behind" each nucleus and so
tends to pull each of the two nuclei away from the other and actually
weaken the bond between the two nuclei.
117
118
119
Molecular Orbital diagram of N2

120
Steps to follow

121
Molecular Orbital diagram of N2

122
123
In N2 molecule , the two nitrogen's are connected using a
triple bond. Its bond energy is high and molecule is highly
stable.

124
Molecular Orbital diagram of N2+

125
Calculate the bond order of N2+ and comment on its stability

• Number of bonding electrons = 9

• Number of antibonding electrons = 4
• Bond order = 9-4/2 =2.5 ( B.O can be fractional also)
• B.O is lower than that of N2, so stability also less
• This species is paramagnetic because of unpaired electron
• Hind: For species N2- , an extra electron will be added to
antibonding orbital. B.O changes, bond strength also changes.

126
Molecular Orbital diagram of NO (Nitric Oxide)

127
 Practice Problem

Calculate the bond order of nitric oxide and predict its

magnetic property

128
 Bonding in Transition metals

• Transition metals are defined as those elements that have (or

readily form) partially filled d orbitals.
• The electronic configuration of the atoms of the first row
transition elements are basically the same. There is a gradual
filling of the 3d orbitals across the series starting from
scandium. This filling is, however, not regular, since at
chromium and copper the population of 3d orbitals increase by
the acquisition of an electron from the 4s shell.

129
D block elements

130
 Electronic Configuration of Transition Elements

For example, the electron configuration of scandium, the first

transition element, is [Ar]3d14s2. Remember that the
configuration is reversed from the fill order—the 4 s filled before
the 3 d begins.
It can be noted that in some of these elements, the configuration
of electrons corresponds to (n-1)d5 ns1 or
(n-1)d10 ns1. This is because of the stability provided by the half-
filled or completely filled electron orbitals.

131
132
 What are complexes?

A metal complex consists of a central metal atom or ion that is bonded to one
or more ligands, which are ions or molecules that contain one or more pairs of
electrons that can be shared with the metal. Metal complexes can be neutral or
charged. A metal ion in solution exists in combination with ligands such as
NH3, Cl- or H2O giving rise to complex ions or coordination compounds.
These complexes contain a central atom or ion, often a transition metal, and a
cluster of ions or neutral molecules surrounding it. Ligands act as Lewis bases
and the central atom acts as a Lewis acid.
Examples: [Co(NH3)6]Cl3, [Fe(C2O4)3]K3, [NiCl4]2− , [CuNH3Cl5]3− [Co(NH3)5Cl]SO4

133
 VALENCE BOND THEORY OF COORDINATION COMPLEXES

• The suitable number of atomic orbitals of central metal ion (s, p, d)

hybridise to provide empty hybrid orbitals.
• This would lead to a yield a set of equivalent orbitals of definite geometry.
• These include octahedral, tetrahedral, square planar and other such
geometrical arrangements.
• These hybrid orbitals accept lone pair of electrons from the ligands and are
directed towards the ligand positions according to the geometry of the
complex.
• The hybridised orbitals can overlap with the ligand orbitals. These orbitals
are ready to donate valence electrons / electron pairs for bonding.

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When inner d-orbitals i.e. (n-1) d orbitals are used in
hybridization, the complex is called – inner orbital complex.
A substance which do not contain any unpaired electron is not
attracted by magnet. It is said to be diamagnetic. On the other
hand, a substance which contains one or more unpaired electrons
in the electrons in the d-orbitals, is attracted by a magnetic field .
It is said to be paramagnetic.

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 Types of ligands

• There are two types of ligands namely strong field and weak field ligands. A strong
field ligand is capable of forcing the electrons of the metal atom/ion to pair up (if
required). Pairing is done only to the extent which is required to cause the
hybridization possible for that Co-ordination number (avail some empty orbitals for
accepting electrons from ligands). A weak field ligand is incapable of making the
electrons of the metal atom/ ion to pair up.
• Strong field ligands : CN–, CO, en, NH3,H2O, NO–, Py.
• Weak field ligands : I–, Br–, Cl–, F–, NO3–, OH–, C2O42–, NH3, H2O

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Valence bond theory applied to the hexaammine chromium (3+) cation

137
It has an octahedral shape, with six dative Cr-N bonds. In
order to explain the six dative Cr-N bonds we would need
to overlap six empty chromium valence orbitals with six
filled valence orbitals of N. We can see that the six
ammine ligands have one electron lone pair each that can
serve as the valence orbitals. Does chromium have six
empty valence orbitals? In order to assess this, we need
first know the oxidation state of the chromium. It is +3
because the ligands are all neutral when the bonds are
cleaved heteroleptically, and the complex cation has a 3+
charge. Therefore, the chromium is a Cr3+ cation.

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Next, we need to know the electron configuration of the Cr3+. A
neutral Cr atom has the electron configuration 4s13d5. When a
transition metal loses electrons to form a cation, it always loses
its two valence electrons first, and then its d electrons. For
chromium this means that we must remove the one 4s electron,
and two of the five 3d-electrons. The three remaining 3d
electrons are expected to be spin up in three different d orbitals
according to Hund’s rule. How many empty valence orbitals
remain? These would be two 3d and the 4s orbitals. In
addition, it would also be justified to consider the three 4p
orbitals as valence orbitals because the 4p orbitals are
energetically only slightly higher than the 4s orbital. That
means that we would have the six valence orbitals that we
would need to explain the six bonds. 139
There is, however, a complication. The six bonds in the complex are not
distinguishable, but the six valance orbitals in the Cr3+ ion are
distinguishable, for example, the 3d orbitals have different shape and
energy than the 4s orbital, which is different from the 4p orbitals.
Therefore, if we overlapped these orbitals with the electron lone pairs at N,
the bonds would not be equivalent, or indistinguishable. We would have
difficulty to explain the highly symmetric octahedral shape of the
molecule. To go around this issue, valence bond theory uses the concept of
hybridization. In this concept we mathematically mix the wave functions
of the valence orbitals to form hybridized orbitals. In our example we
would mix the two empty d-orbitals, the 4s orbital, and the three 4p
orbitals to form six so-called d2sp3 hybridized orbitals. They have the same
shape and size, and their lobes point toward the corners of an octahedron.
Therefore, we can now create overlap between these six orbitals, and the
six electron lone pairs at N to form six equivalent, indistinguishable Cr-N
bonds. We conclude that we have now satisfactorily explained the bonding
and the shape of the complex.

140
Valence bond theory applied to the tetrahydroxo zincate (2-) complex

141
Square Planar Complex
Tetracyanonickelate (2-)

142
In the valence bond picture we view the Ni-CN bonds as
dative bonds, and the complex is considered an adduct of
Ni2+ and CN-. To explain the four bonds, the Ni2+ ion would
need to have four empty valence orbitals. Ni is a group 10
metal and a neutral Ni atom has the electron configuration
4s23d8. To create a Ni2+ ion we must remove the two 4s
electrons, and thus the Ni2+ has the electron configuration
3d8. Do we have four empty orbitals available? Yes, the 4s
and the three 4p orbitals are empty but again they are not
equivalent and thus not suitable to explain four equivalent
Ni-C bonds. Can we hybridize these orbitals? Yes, we can,
but the resulting four sp3 hybridized orbitals would not be
suitable to explain the square planar shape, only the
tetrahedral shape. What valence bond theory suggests in
this case is to reverse the spin of one of the unpaired d
electrons and move it into the other half-filled d-orbital. 143
This produces an empty d-orbital that we can now hybridize
with the 4s and two of the 2p orbitals to four dsp2-hybridized
orbitals. These four orbitals have the property that their lobes
point toward the vertices of a square, thus they are suitable to
explain the square-planar shape. We can approach the ligands
now on the bond axes to create orbitals overlap between the
empty dsp2 Ni and the electron lone pairs of the ligands. We
also say that the ligand donates its electron lone pairs into the
hybridized metal orbitals. This produces the four covalent
bonds that we need and yields a molecule of a square planar
shape.

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 What are Inner Orbital Complexes

• Inner orbital complexes are coordination compounds

composed of a central metal atom having hybridization of the
atomic orbitals including d orbitals of inner shell and s, p
orbitals from the outer shell. In other words, the central metal
atom of these complexes uses inner shell d orbitals for the
hybridization of atomic orbitals. Therefore, these d orbitals are
in a lower energy level than s and p orbitals.
• The most common hybridization of the metal atom in inner
orbital complexes is d2sp3. But there can be some other
hybridizations as well, such as dsp2.

145
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147
 What are Outer Orbital Complexes

• Outer orbital complexes are coordination compounds

composed of a central metal atom having hybridization of the
atomic orbitals including s, p and d orbitals from the outermost
shell. Here, all atomic orbitals involved in the hybridization
are in the same energy level. Since the d orbitals involved in
this hybridization are located outside the s and p orbitals, the
complexes formed from these metal atoms are called outer
orbital complexes.
• The most common hybridization that can be observed in this
type of complexes is sp3d2.

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150
Geometry and magnetic nature of some of the complexes

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