 INORGANIC CHEMISTRY III (Chem3081)

PRESENTATION CONTENTS

 UNIT 1. Symmetry and Group Theory

 UNIT 2. Coordination Chemistry

 UNIT 3. Organometallic Chemistry

 UNIT 4. Bioinorganic Chemistry

4/26/2023 Chem3081 1
 OBJECTIVES OF THE STUDIES


 By studying this unit we come across many of the things

which you are not aware of :
 The significance of group theory
 The process of placing a molecule into a symmetry
 It allows you to determine that Which vibrational
transitions are allowed or forbidden on the basis of
symmetry.
 How EMR interact to show different phenomenons like
polarization, Dispersion, Refraction etc.
 What is Transition & transition probability.

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 UNIT ONE
1. Symmetry and Group Theory
INTRODUCTION
 Group Theory is a mathematical method by which aspects of
a molecules symmetry can be determined.
 The symmetry of a molecule reveals information about its
properties (i.e., structure, spectra, polarity, chirality, etc…).
 It can be grouped into three categories:
Getting to know groups: contain explicit definitions and
examples of groups
Group applications: to understand applications of group
theory.
Group history : focuses on the history of group theory
3

 symmetry operations.
 Symmetry is a fundamental concept of major importance
in art, mathematics, and all areas of natural science.
 In the context of chemistry, once we know the symmetry
of a molecule, it is often possible for us to draw qualitative
information about its physical and chemical properties.
 Then again, we must also express them scientifically. This
could be done with help of symmetry elements & symmetry operations.

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 Cont...d
 It is the relationship between parts of an object

with respect to size, shape and position. Or

 It can also be defined as a harmony or balance in

the proportion or parts to the whole.

 It is a powerful mathematical tool for understanding

structure and properties of molecules.

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 Symmetry Operations and Symmetry
Elements
 A symmetry operation is an action that leaves an object

looking the same after it has been carried out. That

is, an object exhibits symmetry if we can either rotate,
reflect, or invert it etc, without changing its appearance.

Therefore, the process of doing the rotation, reflection

or inversion etc is called symmetry operation, if it does

not change the appearance of the molecule/object.

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 It is also called non-translational movement of
an object that produces a new orientation that is
indistinguishable from the original object.
Example 1: Look at the rotation of the following object by 900

 Orientation A is indistinguishable from Orientation B, but

not necessarily identical. Hence these are Equivalent
Configurations.

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Example 2: Consider the molecule of water: Take a molecule
of water and rotate it by 180° about an
axis passing through the central O atom (between the two
H atoms). After a rotation, it will look the same as before.

☞ ☞ So rotation of water molecule by 180° about an axis

passing through the central O atom is a symmetry
operation. 4/26/2023 Chem3081 8
Example 3: Consider again the rotation of the following
object by 1200;

1200

☞ ☞ After the operation is performed, the object

appears equivalent to the original one.
Example 4: Look again, BF3 molecule

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 All these symmetry operations are performed about
a symmetry element.
Symmetry Element
A Symmetry element is a geometrical entity (axis, point,
line or plane) with respect to which the symmetry
operation is performed.
Hence,
 Each symmetry operation has a corresponding
symmetry element.
 All these operations leave at least one point of the
molecule unmoved.
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Example 1:
In a rotation, the line of points that stay in the same
place constitute a symmetry axis; in a reflection the
points that remain unchanged make up a plane of
symmetry.

Fig. H2O molecule under different operation

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  The following figure shows coordinate system and
symmetry elements of the water molecule.
C2

z
(xz)

y O

H H
x
(yz)

Example2: The B-F1 bond can be defined as an element for BF3

Note: The rotated molecule is4/26/2023

indistinguishable.
Chem3081 12
  The symmetry elements that a molecule may possess
are given in table below.
Symmetry Symbol Description of symmetry
Element operation
Identity E Leaves the system unchanged

Center of i Inversion through the center of

symmetry symmetry

Rotation axis Cn Rotation about the Cn axis by

2/n
Mirror plane  Reflection through the plane

Improper Sn Rotation by 2/n followed by

rotation reflection across a mirror plane
perpendicular to the rotation axis.13
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 1. Identity Element, E
 The identity operation does nothing to a molecule and
so leaves any molecule completely unchanged.
 The identity operation is given the symbol E.
(E from Einheit = Unity, un object is left unchanged)
 It is the simplest symmetry operation and all molecules
contain this element.
 It is equivalent to multiplying a number by 1 or adding
0 to a number, in algebra.
Example:

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I. C1 operation (rotation by 360°)
☞ Results in the same molecule that we have started
with. Because it does nothing or has no effect. Hence
it is an identity operation.
II. Two consecutive C2 (rotation by 1800) operations about
the same axis result in identity.
i.e. C2 x C2 = C22 = E
III. Likewise three consecutive C3 operation,
i.e. C3 x C3 x C3 = C33 = E
 The product of multiple symmetry operations can
give the identity.
   Successive operations leads to identity (Cnn = E).
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Example: Consider the following

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 2. Rotational axis, Cn
 A simple rotation about an axis passing through
the molecule.
 That is, if rotation of a molecule by 360o/n results in
an identical configuration, the molecule is said to have
an n-fold rotational axis (or n-fold axis of rotation).
 It is denoted as Cn
 Cn is a rotation of (360/n), where n is order of the
rotation. Or
(It is called the total number of operations).
Hence, C2 = 180° rotation, C3 = 120° rotation, C4 = 90°
rotation, C5 = 72° rotation, C6 = 60° rotation, …
   C2 is called a binary rotation
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Example 1:
H2O molecule possesses two-fold rotation axis, i.e. if the
operation is performed twice all the atoms are back to
their initial position.
   Therefore, H2O molecule has a C2 axis.
 Hence, rotation by 1800(2/n, n = 2) is a symmetry
operation and the axis about which the rotation
takes place is the symmetry element.
☞☞ A Cn axis is often called a "proper" rotational axis
and the rotation about it is a "proper" rotation
(one or more rotations about the axis).

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☞ When n > one, symmetry axis exist. So some molecules
have more than one Cn axis, hence the one with the
largest value of n is called the principal axis, and is
usually the z-axis.
 Note that by convention rotations are counterclockwise
about the axis.
Example 2:

Fig. The C2 axis in trans-dinitrogen difluoride

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 3. Reflection Operation, 
 It is an operation where the shape (molecule) is reflected
through a mirror plane.
 It contains a mirror plane that divides a molecule into
mirror image halves.
 The reflection operation is given the symbol σ.
 If reflection of all parts of a molecule through a plane
produced an identical configuration, the symmetry
element is called a mirror plane or plane of symmetry.
 Atoms lying in a plane is a special case since reflection
through a plane doesn’t move the atoms.
  Consequently all planar molecules have at least one
plane of symmetry ≡ molecular plane.
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 Note: σ produces an equivalent configuration. Hence, σ2 =
σ.σ, produces an identical configuration with the original
∴ σ.σ = σ2 = E
∴ σn = E for n even; n = 2, 4, 6,…
σn = σ for n odd; n = 3, 5, 7,…
 Mirror planes are classified as:-
1. Vertical reflection plane, σv: planes that contain (or
parallel to) the principal rotational axis.
2. Horizontal reflection plane, σh: planes that are
perpendicular to the principal rotation axis.
3. Diagonal reflection plane, σd: is parallel to the principal
rotation axis, but bisects the angle between a pair of
2-fold rotation axes. It is also called dihedral.
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 Example: Vertical reflection plane
☞ Consider the effect of a vertical reflection on Fe(CO)5.
 In this case we have defined the symmetry element as
the plane containing CO1, CO3 and CO5.

Vertical reflection plane - plane collinear with principal

axis- lie on the same axes.
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☞☞ Note that CO2 and CO4 switch positions as a result.
Example: Horizontal reflection plane
The horizontal reflection plane does not change the
position of any of the atoms in BF3 since all of the atoms
are in the mirror plane.

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However, we can see a case where the horizontal plane of
reflection results in a change in the two axial carbonyls,
but not the equatorial carbonyls, as shown below.

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 4. Inversion, or Inversion Center, i
 It involves passing each atom through the center of
the molecule. That is,
☞☞ If an atom has coordinate (x, y, z) then it has
coordinates (-x, -y, -z) after inversion.

 All points in the shape (molecule) are reflected though

a single point.
 The point is the symmetry element for inversion.
 This turns the molecule inside out in a sense.
 If an atom exists at the inversion centre it is the only
atom which will not move upon inversion.
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 All other atoms occur in pairs which are “twins”. This
means no inversion centre for molecules containing an
odd number of more than one species of atoms.
i2 = ii = E
⇒ in = E , where n even
in = I, where n odd
Example: A molecule such as Mo(CO)6 does have a center
of symmetry and can be inverted as shown below.

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 Other molecules that has an inversion center

Inverts all atoms through the centre of the object.

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 5. Improper Rotation, Sn or rotation-reflection)
 It is a composite operation-occurring in two steps:
i.e. rotation of the molecule through a certain angle
followed by a reflection in the plane perpendicular
to the rotation axis.
 The symbol Sn, where n is order of the rotation.
 The symmetry element for Sn is the rotation axis.
 The rotation-reflection operation consists of rotating
through an angle 360°/n about the axis, followed by
reflecting in a plane perpendicular to the axis.
Note: S1 is the same as reflection , and
S2 is the same as inversion
Example: Consider four-fold improper4/26/2023
rotation,
Chem3081
S4 in CH4. 28
 The operation consists of 90° rotations about an axis
bisecting two HCH bond angles, followed by a reflection.
 However, neither the 90° operations nor the reflection
alone is a symmetry operation for CH4.
 Therefore, the accurate definition of improper
rotation is a proper rotation followed by inversion.

  All planar molecules have an Sn

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Example: Identify the symmetry elements in the BF3
molecule.

a. Rotation relative to an axis perpendicular to the plane of

the molecule through the B atom by 120° will move
Fa to Fb, Fb to Fc, Fc to Fa and B into itself.
a. Also rotation by 240° will move Fa to Fc, Fc to Fb, Fb to Fa
and again B into itself so BF3 has a C3 axis.
c. Rotation relative to an axis through Fa and B by 180° will
exchange Fc and Fb while Fa and B go into themselves.
Likewise such axes exist through Fb and B as well as Fc and
thus, BF3 has three C2 axes perpendicular to the C3 axis.
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 d. A mirror plane through Fa and B will also exchange Fb and Fc while Fa and B
are reflected into themselves. Such mirror planes also exist through Fb
and B as well as Fc and B.
 Thus, BF3 has three mirror planes designated as v since
they are coincident with the C3 axis.
 Note that the C3 axis is the principle axis since it has the highest n value.
e. BF3 also contains a mirror plane designated as h which is
the plane of the molecule such that all atoms are
reflected into themselves.
f. Finally, if the molecule is rotated by 120° and reflected in the plane of the
molecule all atoms go into themselves or equivalent atoms (in this case, since
the molecule is planer, same result as C3). Thus, the molecule also possesses an
S3 axis.

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 Summary:
 An S1 axis - a rotation through a full 360° followed
by a reflection in the horizontal plane is equivalent
to a horizontal reflection alone. Therefore,
☞ S1 and σh are the same. So the symbol σh is used
instead of S1.
Similarly,
☞ An S2 axis - a rotation through 180° followed by
reflection in the horizontal plane is equivalent to an
inversion, and the symbol i is used rather than S2.
Shortly,
S1 is equivalent to σ, and S2 is equivalent to i.
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 Multiple Application of Symmetry Operations
 Symmetry operation can be applied multiple times.
For example, a C3 rotation may be applied twice.
Returning to BF3 we can consider C32 rotation, which
consists of two applications of the C3 rotation.

C32 = C3C3
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 If we apply the C3 rotation one more time (for a total of
three applications) the geometry returns to the starting
structure. In other words we can write: C33 = C3C3C3 = E

 In multiple operation, the order of operation matters:

 In general the order of operation will affect the final
result. In this case the operators do not commute.
i.e. for two symmetry operations A and B, AB is not
necessarily the same as BA. 4/26/2023 Chem3081 34
Example:

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Other Examples: Consider the following figure

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But

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What about C34 ?

⇒ Only C , C
3
2,
E are separate and distinct operations.
3
Similar arguments can be applied to any proper axis of
order n.
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 The Symmetry Point Groups
A group, G
 Any set or collection of elements, which together with
some well defined combining operation that obey
a certain set of rules is called a group. Or
 A group, G is a set of elements A, B, C, ... connected
by a combination rule (written as a product, for
example A.B).
Properties of a Group
 Elements of a group must obey the following rules:
R 1. Combination of any two elements of the group must
produce an element which is also a member of the group.
This is the closure property. 4/26/2023 Chem3081
☞ For all elements A and B of the group G, A.B = C; is also
an element of the group G.
Mathematically  Closer property of sets.

 The group multiplication table must be closed.

Example: Consider H2O, which has E, C2, 2σv′s symmetry
elements.
☞ The group multiplication table is given as follows. And
☞ The operations written along the first row of the table
are carried out first, followed by those written in the
first column.

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 First operation

C2V E C2 σV σ’V

E E C2 σV σ’V
Second operation
C2 C2 E σ’V σV

σV σV σ’V E C2

C2 E
σ'V σ’V σV

R 2. The combination rule (the binary operation) must be

associative, i. e. A.(B.C) = (A.B).C
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R 3. There must be an element, called the identity E (also
called unity), such that E.A = A.E = A, for all elements A
of the group.
R 4. Every element A must have an inverse, A−1 which is
also a group element such that A.A−1 = A−1.A = E
Note that
 In ordinary algebra, we may say that multiplication
is commutative, i.e. AB = BA. However, in group
theory, the commutative theory does not hold in
general.
 Thus AB may give C, while BA may give D, where C & D
are two more elements in the group.
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Summary
Shortly, the above rules are summarized as properties
of groups.
1. The closure property holds.
2. The associative property holds.
3. Each group must have an identity element.
4. Each group must have an inverse.

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 Point groups
 The symmetry operations that characterize the various
different shapes of molecules define mathematical
groups referred to as point groups. Hence,
 Molecules that possess the same set of symmetry
elements belong to the same point group.
 It is also convenient to classify molecules with the same
set of symmetry elements by a label.
So that molecules with the same label belong to the
same point group.
Example: Consider symmetry elements of H2O molecule.
We find that it has: E, One C2 axis, & Two σv planes.
4/26/2023 Chem3081 44
 The set of this four symmetry operations generated by
these elements is said to form a symmetry group or
point group. Therefore, they characterize the point
group C2v for water.
 Point groups get their name from the fact that at
least one point in space remains unchanged for all
operations in the group.
Classification of point groups
 When we say a molecule belongs to a certain point
group, it means that the molecule possesses a specific,
self-consistent set of symmetry elements.
 The most common point groups are described below
with illustrative examples. 4/26/2023 Chem3081 45
 1. Point Groups with low symmetry
 Groups that possess only one or two symmetry elements.
These are: C1, Ci and Cs.
 C1: has only identity element: In other words there is
no symmetry.
 Cs: has identity and a mirror plane alone: The symmetry
is restricted to a mirror plane.
 Ci : has identity and inversion center alone.
2. Point Groups with high symmetry
 These are groups with a large number of characteristic
symmetry elements. This includes: Octahedral, Oh,
Tetrahedral, Td & Icosahedra, Ih.
4/26/2023 Chem3081 46
 3. Point Groups with an n-fold rotational axis, Cn
 After groups with high or low symmetries have been
eliminated by inspection, the remaining point groups
should be assigned by looking for characteristic
symmetry elements, such as an n-fold rotation axis.
 These groups include the groups: Cn, Cnv & Cnh
Cn: it has identity & n-fold rotation axis.
Cnv: identity, Cn axis & vertical mirror planes, σv..
Cnh: identity, an n-fold rotation axis and a horizontal
mirror plane, σh.

4/26/2023 Chem3081 47
 Note that presence of certain symmetry elements may
be implied by the presence of others; thus in C2h, the
operations C2 and σh jointly imply the presence of a
center of inversion, i.
4. Dihedral point groups
Molecules possessing nC2 axes perpendicular to the
principal axis. These group includes: Dn, Dnh and Dnd
 Dn: If there are no mirror planes, the molecule belongs
to the Dn point group.
 Dnh: The presence of a mirror plane perpendicular to
the principal axis results in the Dnh point group.
 Dnd: In addition to the elements of Dn, possesses n
diagonal mirror planes, σd.
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 Determining the Point Group
Summarized rules for classification of molecules in to
point groups.
 The number & nature of the symmetry elements in a
given molecule are denoted by its point group.
 The point group has labels such as Cn, Cnv, Cnh, Dn,
Dnh, Dnd etc.
 These symbols are called the Schonflies Symbols.
 These point groups are conventionally divided in to:
C groups, D groups & Special groups.
Therefore, using these symbols and based on the
following rules we can classify molecules in to point groups.
1. Determine whether the molecule belongs to a special
group such as: Td, Oh, Ih , Dh, or Cv Chem3081
4/26/2023 49
 ☞ If the molecule is linear, it will be either Cv or Dh..
☞ If it has infinite number of two-fold rotation axes
perpendicular to the Caxis, it will fall in to point
group Dh; if not, it is Cv.
2. If the molecule is not linear, it may belong to a point
group of high symmetry: Td, Oh, or Ih.
3. If 1 or 2 is not found to be the case, look for a proper
axis of rotation of the highest order in the molecule.
☞ If none is found, the molecule is of low symmetry,
falling in to point group: Cs , Ci , or C1.
☞ The presence of mirror plane or an inversion center
will distinguish among these point groups.
4/26/2023 Chem3081 50
4. If Cn axes exist, select the one of highest order. If the
molecule also has S2n axis, with or without an
inversion center, the point group is Sn.
5. If no Sn exists, look for a set of n two-fold axes
perpendicular to the major Cn axis.
☞ If no such set is found, the molecule belongs to
either of Cn , Cnh, or Cnv.
☞ If σh plane exists, it is of Cnh point group even if
other planes of symmetry are present.
☞ If no σh plane exists and a σv plane is found, the
molecule belongs to Cnv point group.
☞ If neither the horizontal nor the vertical planes
are found, the point group is4/26/2023
simply Cn.
Chem3081 51
 6. If in (5) nC2  to Cn is found, the molecule belongs to
either Dn, Dnh, or Dnd point group.

Example 1: Consider, for instance, the bent triatomic

molecule of the type AB2 (e.g. H2O).
• H2O is not linear and nor does it belong to any of the
special groups.
• It does, however, possess a C2 axis.
• C2 axis is the highest order proper axis in the molecule,
and there is no S4 axis.
• No C2 axes  to the C2 already considered; hence
H2O must belong to a C-type point group.
• Since, there is no σh, so the C2h group is ruled out.
4/26/2023 Chem3081 52
• There are two σv‘s, one is the molecular plane and the
other is perpendicular to it.
 Hence, H2O belongs to the C2v point group.
Example 2. Consider the pyramidal molecule of type AB3
such as NH3.
• The molecule is not linear.
• Does not belong to one of the other special groups.
• Possess a C3 axis of rotation but none is of higher order.
• There is no S6 axis
• No C2 axis  to the C3 axis is found.
• Therefore, the point group must be one of the C-types
i.e. either, Cn, Cnh, Cnv.

4/26/2023 Chem3081 53
 • No σh, so the possibility of C3h is ruled out.
• But there are three σv’s.
 Thus, the point group is C3v.
Alternative Method for Determining Point Group
 There are much quicker ways of assigning the point
group. However, the most popular one is to use a flow
chart.
 The flow chart contains all of the point groups discussed
above as well as a few other not commonly encountered.
 Follow the following flow chart for assigning the point
group.

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4/26/2023 Chem3081 55
4/26/2023 Chem3081 56
 Worked Examples

We illustrate the application of the above chart with

reference to some worked examples
a. Determine the point group of trans-N2F2
START
First draw the structure
Is it linear? No
Is the molecule Td, Oh or Ih no
Is there a principal Cn axis yes
Are there two C2 axes ⊥ to the principal
axis? No.
Is there a σh plane (⊥) to the principal axis?
Yes. STOP Here
SO, the point group of trans-N2F2 is C2h.
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Applications of Symmetry

There are several applications of the group theory in classification of

molecules. Some of this are:

 optical activity -Chirality or achirality,

 polarity,

 IR & Raman spectra,

 It helps to identify types of orbitals used in bonding.

Definition 1: Polar molecules are molecules with a permanent electric

dipole moment.

However, there are symmetry elements that rule out the presence of a
4/26/2023 Chem3081 58
permanent electric dipole in molecules.
1. Molecule cannot be polar if it has an inversion center.

Example: H2O is polar (no i) , SF6 is non-polar (has i ).

Inversion center molecule has matching charge distributions  no

dipole moment.

2. For the same reason, a dipole moment cannot lie  to mirror

plane or rotation axis.

 Because, mirror plane demands identical atoms on either side of

the plane, so there can be no dipole moment across a plane

4/26/2023 Chem3081 59
 Generally, a molecule cannot be polar if it belongs to any of the following
point groups.

1. Group that has an inversion center.

2. Groups D and their derivatives.

3. Cubic groups (Td, Oh), icosahedral (Ih) group, and their

modifications. Example: BF3 (D3h), SF6 (Oh) , CCl4 (Td), PCl5 (D3h) are
nonpolar.
Definition 2: Chiral molecule is a molecule that cannot be superimposed
on its own mirror image. Or Molecules that are not superimposable on
their mirror images are labeled as chiral or dissymmetric.

 Chiral molecules are optically active i.e. they can rotate the plane of
polarized light.
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 A chiral, molecule and its mirror image partner are called
enantiomers.
 Enantiomeric pairs can rotate the plane of polarized light by
equal amounts but in opposite directions.
 According to group theory, for chirality the molecule should not
have an improper rotation axis.
 Generally, a molecule is not chiral if
1. It possesses an improper rotation axis, Sn.
2. It belongs to the groups Dnh or Dnd (but it may be
chiral if it belongs to the groups Dn).
3. It belongs to Td or Oh.
Example: SiCl4 or Ni(CO)4 belongs to Td  are not
4/26/2023 Chem3081 61
chiral.
► Remember that, mirror plane alone is equivalent to an S1
axis and inversion center is equivalent to an S2 axis.
► Therefore, molecules with either σ or i have improper
rotation axes and hence cannot be chiral.
► Note that, a higher-order improper-rotation axis is not also
present.
Example: quaternary ammonium ion has neither a
mirror plane (S1) nor an inversion center (S2), but it
does have an S4 axis. So it is not chiral.

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