Qualitative Treatment of Molecular Orbital Theory

CHE 212
SELECTED TOPICS IN CHEMISTRY FOR CHEMICAL

ENGINEERING 1
BY
DR. A. A. AKINSIKU
CHEMISTRY DEPARTMENT
COLLEGE OF SCIENCE & TECHNOLOGY
BONDING IN COORDINATION CHEMISTRY
The structural theories based on modern principles
of bonding are;
1.Valence Bond Theory (VBT)
2.Crystal Field Theory (CFT)
3.Molecular Orbital Theory (MOT)
According to Werner’s theory (1935)
• ligand donates electron pairs to metal ions or

atoms to form coordinate linkages.
• shapes and magnetic behaviour of metal
complexes
• Ligands: Lewis bases
• Transition metal ion: Lewis acid
• Co(NH3)63+
• Pt(NH3)3Br+
Valence Bond Theory /Pauling’s Theory of
Complexes (VBT),
• useful in predicting some of the chemical and
physical properties of complexes.
• But it failed to explain some facts.
Crystal Field Theory (CFT)
• Description of metal-ligand interaction and is
especially helpful in explaining the visible
absorption spectra of metal complexes.
Molecular orbital theory (MOT)
• most exact theory
Each theory has advantages and disadvantages
Shapes
• All atoms have sets of bound and continuum
s, p, d, f, g, etc. orbitals
• Some of these orbitals may be unoccupied in the
atom's low energy states, but they are still present
and able to accept electron density if some
physical process
Figure 1. Molecular orbitals of hydrogen. left: bonding MO,
right: antibonding MO
Qualitative Treatment of Molecular Orbital
Theory (MOT)
• Quantum mechanical methods describe how
atoms are held together in molecules.
• Fundamental principle of MO theory gives
insights into the nature of chemical bonding as it
proposes that:
• Electrons belong to the entire molecule:
• Individual electron pairs are found in molecular
orbitals that are distributed over the entire
molecule.
• The theory incorporates the wave like
characteristics of electrons in describing bonding
behaviour.
• It takes into account the covalent character of
metal to ligand bond.
You need to know:
 Atomic orbitals combine to form molecular
orbitals which surround the molecule
 Molecular orbitals are wave functions giving the
probability of finding an electron in certain regions
of a molecule.
 Each molecular orbital can only have 2 electrons,
each with an opposite spin.
• When two or more degenerate (same energy)
molecular orbitals are available, one electron is
placed in each before any one of them gets two
electrons.
• When two atomic orbitals combine to form a
molecular orbital, the wave functions are
combined both in phase and out of phase to
create one bonding molecular orbital.
An antibonding molecular orbital (*)
• occurs when electron density of the orbital is
concentrated in regions of space outside the area
between the atomic nuclei.
• higher energy than the atomic orbitals of their
constituent atoms.
• When antibonds are formed, the interaction
creates a decrease in the intensity of the negative
charge, which causes a decrease in the plus minus
attraction in the molecular bond.
2py Orbitals
16
Sigma Bonds (σ)
• occurs when the majority of the electron density is
found on the bond axis
• results from the overlap between two 1s orbitals,
as rotating sigma bond does not decrease the
overlap of the orbitals involved a sigma bond can
rotate freely about the bond axis.
• two types of sigma orbitals formed:
antibonding sigma orbitals (σ*) and
bonding sigma orbitals (σ).
Pi Bonds ()
• occurs when the majority of the electron density is
found above and below the bond axis.
• results from the overlap of two 2p orbitals that are
parallel to each other,
• The pi bonding bonds as a side to side overlap,
which then causes no electron density along the
axis, but there is density above and belong the axis.
Pi Bonds
Drawing Molecular Orbital Diagrams
The order of molecular orbitals in simple
mononuclear,
diatomic molecule is:
σ1s, σ*1s, σ2s, σ*2s, σ2px, π2py, π*2py, π2pz, π*2pz,
σ*2px , σ3px, π3py π*3py, π3pz, π*3pz, σ*3px
Drawing Molecular Orbital Diagrams (Cont.)
1. Determine the number of electrons in the
molecule.
2. Fill the molecular orbitals from bottom to top
until all the electrons are added.
3. Describe the electrons with arrows. Put two
arrows in each molecular orbital, with the first
arrow pointing up and the second pointing down.
4. Orbitals of equal energy are half filled with
parallel spin before they begin to pair up.
Determining Bond Order
Bond Order= (a-b)/2
where ...
a= number of e- in bonding Molecular Orbitals
b= number of e- in antibondng Molecular Orbitals
Bond Order indicates the strength of the bond.
Bond Order indicates the strength of the bond
Determining the Stability of the Molecule:
1. If the Bond Order is Zero, then no bonds are
produced and the molecule is not stable (for
example He2).
2. If the Bond Order is 1, then it is a single covalent
bond. The higher the Bond Order, the more
stable the molecule is.
3. An advantage of MOT when it comes to Bond
Order is that it can more accurately describe
partial bonds (for example in H2+, where the Bond
Order=1/2), than Lewis Structures.
Example
Draw the molecular orbital diagram for:
1. diatomic hydrogen molecule, H2,
2. diatomic helium molecule, He2 ,
3. Diatomic oxygen molecule, O2.
• How stable are the molecules?
• Determine the magnetic character of each
molecule.
Solution
1. The molecular orbital diagram for a diatomic
hydrogen molecule, H2, is
• Bond Order = 1/2(2 - 0) = 1

• The bond order above zero, so H2 is stable.
• Because there are no unpaired electrons, H2
is diamagnetic.
3. The molecular orbital diagram for a diatomic oxygen molecule, O2 is
 Bond Order = 1/2(10 - 6) = 2

 The bond order is two so the molecule is stable.
 There are two unpaired electrons, so molecule is paramagnetic.

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CHE 212

SELECTED TOPICS IN CHEMISTRY FOR CHEMICAL

• ligand donates electron pairs to metal ions or

• Bond Order = 1/2(2 - 0) = 1

 Bond Order = 1/2(10 - 6) = 2

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