Topics

Introduction
Molecular Structure and Bonding
Molecular Symmetry
Coordination Complexes
Electronic Spectra of Complexes
Reactions of Metal Complexes
Organometallic Chemistry

Symmetry
Powerful mathematical tool for understanding
structures and properties
Use symmetry to help us with:
Detecting optical activity and dipole
moments
Forming MOs
Predicting and understanding spectroscopy
of inorganic compounds
Infrared, Raman and UV-visible

Symmetry and Your Text(s)

Symmetry tools and language
Sec 4.1-4.4 (Atkins)
3.1-3.6, 4.4 (Housecroft)
Flow chart p.122 (Atkins)
p.81 (Housecoft)

Bonding Theory
Sec 4.5-4.7 (Atkins)
Box 4.1, sec 4.5-4.7 (Housecroft)

Symmetry and the Exam

Recognize symmetry elements
Identify the important elements present in a
molecule
Assign the point group of an object or
molecule
Read a character table

Symmetry Elements
A symmetry element is present if the
operation is performed and the object is
indistinguishable from its original state
Element

Name

Operation

Cn

n-fold rotation

rotate by 360/n

mirror plane

Reflection through a plane

Center of inversion

Inversion through the center of

the object

Sn

Improper rotation axis

Rotation as Cn followed by
reflection in perpendicular mirror
plane

Identity

Do nothing

Center of Inversion: I
Inverts all atoms through the centre of the
object

Inversion vs Rotation (C2)

Mirror Planes:
Reflection of object through a mirror plane
Objects in the plane are reflected onto
themselves, objects on either side of the plane
are reflected to the other side
Three types
h : Horizontal, perpendicular to principal axis
v : Vertical, parallel to principal axis
d : Dihedral, same plane as v related by half a
rotation of the principal axis

Dihedral vs. Vertical

Typically d and v are related by rotation of
180/n
Labelling:
Exception: when n=2, label is v not d

Rule of Thumb: dihedral planes pass through

fewer atoms (i.e. is dihedral to the angle of
the bonds)

Improper Rotation Axis: Sn

Rotate 360/n followed by reflection in mirror plane
perpendicular to axis of rotation

All planar molecules have an Sn

Special Cases: S1 and S2

S1= h and S2 = i

Comparing Symmetry
Compare NH3 and BF3

Point Groups
collections of symmetry elements are
summarized into Point Groups
these are groups as strictly defined by
mathematical group theory

short form method for identifying all of the

symmetry elements present in a molecule
OC
OC

CO
Mo
CO

CO
CO

Oh

8C3, 6C2, 6C4, i,

3C2, 6S4, 8S6,
3h, 6d

Identifying Molecular Symmetry

Requires knowing molecular geometry
First draw a Lewis structure
Use VSEPR to predict molecular geometry
Use VSEPR geometry to identify symmetry
elements present
Classify molecule according to its point group

Lewis Structures
1. Count valence electrons available, include
net charges.
2. Write skeleton structure, drawing bonds
between atoms using up two valence
electrons for each bond.
3. Distribute remaining electrons to most
electronegative species first to fill electron
shells.
4. Satisfy unfilled octets where possible by
drawing multiple bonds

Resonance Structure and Formal Charge

Resonance allows for non-integer bond order
and delocalized electron distribution
Formal Charge
Predicts which of multiple possible structures are
more favourable

1
FC = group # bonded electrons unshared electrons
2

VSEPR
Relies on the electron distribution around the
central atom
Bonded pairs
Typically ignore bond order (1,2 etc)
Ignore what atom it is bound to
Occupy less volume than lone pair
Lone pairs (on the central atom)
Bulkier than bonds
Have largest impact on molecular geometry

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Examples
trans-CrCl4O2

PCl5

Character Tables
Character tables are tell-all manuals of
symmetry, tabulated in your text
Using group theory, lists of behaviour under
the symmetry elements in a point group are
tabulated, these are called irreducible
representations and they are said to span
the group
Therefore, a portion of a molecule can be
described by some linear combination of
these irreducible representations.

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Reading the Character Tables

C3v

2C3

3v

A1

A2

-1

Rz

-1

(x,y), (Rx,Ry)

x2+y2+z2

(x2-y2,xy)

Character values:
1 means no change
-1 means change of sign
2, 0 sum of multicomponent behaviour

Mulliken Labels
A,B,E,T indicating degeneracy
A vs B : symmetric or antisymmetric wrt highest order
rotation axis
1,2 : symmetric or antisymmetric wrt C2 axis or v
g,u : symmetric or antisymmetric wrt i
, : symmetric or antisymmetric wrt v
MO are labeled with the Mulliken labels using lower
case to differentiate them from irreducible
representations

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D3h Character Table

D3h

2C3

3C2

2S3

3v

A1

A2

-1

-1

Rz

-1

-1

(x,y)

A1

-1

-1

-1

A2

-1

-1

-1

-1

-2

(Rx, Ry)

x2+y2, z2

(x2-y2, xy)

(zx, yz)

Basis Functions
Shows how standard components transform (are
described by which irreducible representation)
x,y,z :corresponds to the behaviour of the px, py,
pz orbitals
x2+y2+z2 : behaviour of an s orbital
xy, xz, yz, z2, x2: behaviour of respective d orbitals
Ri : behaviour of Rotation around axis i

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Degeneracy
When two basis functions are shown in
parenthesis these objects transform together
and are degenerate
eg. (x,y)

They cannot be considered individually and

must be treated as a pair

Applications of Symmetry
Chirality
means non-superimposable on its mirror image
presence of Sn, mirror plane or i all rule out
chirality

Dipole moment (polarity)

a permanent dipole cannot exist if i is present
dipole moment cannot be perpendicular to any
mirror plane or Cn

IR/Raman Spectroscopy
Constructing MOs

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Constructing MOs
typical structure of inorganic compounds involves a
central atom with some arrangement of surrounding
atoms attached to it (ligands)
Build Symmetry Adapted Linear Combinations of
Atomic Orbitals (SALCs) out of groups of atomic
orbitals (from the ligands)
Shown in Appendix 4 of Shriver and Atkins

Combine SALCs with orbitals on the central atom

Recall that only orbitals of the same symmetry can be
combined

We use symmetry to assign and build orbitals and

combinations of orbitals to make complete MOs

Identifying the MO Components

it is helpful to determine in advance how many MOs

of each type and what their symmetry should be
use vectors to represent bonds

use vectors between the atoms for the sigma orbitals

use vectors perpendicular to the sigma orbitals for the pi
orbitals

determine how these vectors transform under the

symmetry of the molecule
determine the irreducible representations which
combine to produce this behaviour
these irreducible representations are the MO labels
now all we have to do is figure out what orbital
combinations they are formed from ....

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Identifying Symmetry Adapted Orbitals

Steps:
1. Identify the point group
2. Arrange the group of ligand orbitals,
determine their transformation under the
symmetry operations of the point group.
3. Assign a symmetry label to the group orbital.
4. Match the labeled group orbitals with atomic
orbitals on the central atom.

Energy Levels of MOs

Can be roughly estimated by
energies of atomic orbitals
degree of overlap

Determine computationally
Recall that our biggest concern is
understanding possible interactions and
populating existing MOELDs

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Conclusions
Symmetry
Identifying symmetry elements
Assigning point groups
Reading character tables
transforms
basis functions
Constructing MOs

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