UNIVERSITY OF EASTERN AFRICA, BARATON

SCHOOL OF SCIENCE AND TECHNOLOGY

DEPARTMENT OF MATHEMATICS, CHEMISTRY AND PHYSICS

TRANSITION METALS AND COORDINATION CHEMISTRY; CHEM402

VBT, MOT ASSIGNMENT

INSTRUCTOR: MR. ABUTO EDGAH

LEARNER: WANYONYI T. WEKESA; SWANTO2111

ASSIGNMENT DONE AND SUBMITTED IN PARTIAL FULFILMENT OF THE

COURSE CHEM402

DUE DATE: 27TH OCTBER, 2023.

 COMPARISON OF VALENCE BOND THEORY (VBT) AND MOLECULAR ORBITAL
THEORY (MOT)
SIMILARITIES:
Valence Bond Theory (VBT) and Molecular Orbital Theory (MOT) have the following common
features:
1. The Basic principle is same in both the theories. Both involve distribution of electrons. Thus
whether it is atomic or molecular cannot have more than two electrons.
2. Both the theories include the sharing of electrons by the nuclei.
3. According to both the theories the energy of overlapping orbitals must be comparable and
there must be similarities in their symmetry.

DIS-SIMILARITIES:
Valence Bond Theory (VBT) Molecular Orbital Theory (MOT)
Bonds are localized to two atoms not molecule. Bonds are localized to two atoms as well as
molecule.
Valence orbital theory was first proposed by Molecular orbital theory was proposed by F.
W.Heitler and F.London in 1927. Hund and R.S. Mulliken in 1932.
Resonance plays an important role in this There is no place of resonance in this theory.
theory.
There is no explanation of paramagnetic Satisfactory explanation of paramagnetic
character of oxygen. character of oxygen.
Calculations are simpler. Calculations are very tedious.
In VBT, two half-filled atomic orbitals combine In MOT, atomic orbitals from each atom
to form a bond between two atoms. combine to form molecular orbitals.
The atomic orbital of combining atoms retains The atomic orbital of combining atoms loss
their identity. their identity in molecular orbitals.
The resonance effect has an important role in The resonance effect has no role in MOT.
VBT.
It fails to explain the paramagnetic character of It explains the paramagnetic character of the
the O2 molecule. O2 molecule.
It fails to explain the formation and existence of It explains the formation and existence of
H2+ion. H2+ion.

Postulates of Valence Bond Theory

1. Covalent bonds are formed when two valence orbitals (half-filled) belonging to two
different atoms overlap on each other. The electron density in the area between the two
bonding atoms increases as a result of this overlapping thereby increases the stability of
the resulting molecule.
 2. The presence of many unpaired electrons in the valence shell of an atom enables it to
form multiple bonds with other atoms. The paired electrons present in the valence shell
do not take participate in the formation of chemical bonds as per the valence bond theory.
3. Covalent chemical bonds are directional and are also parallel to the region corresponding
to the atomic orbitals that are overlapping.
4. Sigma bonds and pi bonds differ in the pattern that the atomic orbitals overlap in, i.e. pi
bonds are formed from sidewise overlapping whereas the overlapping along the axis
containing the nuclei of the two atoms leads to the formation of sigma bonds.

©Formation of sigma bond.

Limitations of valence bond theory

 VBT fails to explain the tetravalency of carbon.

 Valence bond theory does not address the issue of the paramagnetic nature of O2
molecule.
 Failure to explain the formation of molecule with odd electron. Example: H 2+ like
molecule formation.
 No explanation about the bonding in electron deficient compound with incomplete octet
such as B2H6.
 It explains only covalent bonding but not co-ordinate covalent bonding.
 No discussion about the energies of the electrons.

Applications of Valence Bond Theory

 The maximum overlap condition which is described by the valence bond theory can
explain the formation of covalent bonds in several molecules.
 This is one of its most important applications. For example, the difference in the length
and strength of the chemical bonds in H2 and F2 molecules can be explained by the
difference in the overlapping orbitals in these molecules.
  The covalent bond in an HF molecule is formed from the overlap of the 1s orbital of the
hydrogen atom and a 2p orbital belonging to the fluorine atom, which is explained by the
valence bond theory.

Molecular Orbitals

The space in a molecule in which the probability of finding an electron is maximum can be
calculated using the molecular orbital function. Molecular orbitals are basically mathematical
functions that describe the wave nature of electrons in a given molecule.

These orbitals can be constructed via the combination of hybridized orbitals or atomic orbitals
from each atom belonging to the specific molecule. Molecular orbitals provide a great model via
the molecular orbital theory to demonstrate the bonding of molecules.

Characteristics of Bonding Molecular Orbitals

 The probability of finding the electron in the internuclear region of the bonding
molecular orbital is greater than that of combining atomic orbitals.
 The electrons present in the bonding molecular orbital result in the attraction between the
two atoms.
 The bonding molecular orbital has lower energy as a result of attraction and, hence, has
greater stability than that of the combining atomic orbitals.
 They are formed by the additive effect of the atomic orbitals so that the amplitude of the
new wave is given by Φ= ΨA + ΨB
 They are represented by σ, π, and δ.

Characteristics of Anti-bonding Molecular Orbitals

 The probability of finding the electron in the internuclear region decreases in the anti-
bonding molecular orbitals.
 The electrons present in the anti-bonding molecular orbital result in the repulsion
between the two atoms.
 The anti-bonding molecular orbitals have higher energy because of the repulsive
forces and lower stability.
 They are formed by the subtractive effect of the atomic orbitals. The amplitude of the
new wave is given by Φ ´= ΨA – ΨB
 They are represented by σ∗, π∗, δ∗
Why Are Antibonding Orbitals Higher in Energy?

The energy levels of bonding molecular orbitals are always lower than those of anti-bonding
molecular orbitals. This is because the electrons in the orbital are attracted by the nuclei in the
case of bonding molecular orbitals, whereas the nuclei repel each other in the case of anti-
bonding molecular orbitals.

Molecular Orbital Theory

Bonding Molecular Orbitals Anti-Bonding Molecular Orbitals

Molecular orbitals formed by the additive effect Molecular orbitals formed by the subtractive effect of
of the atomic orbitals are called bonding atomic are called anti-bonding molecular orbitals.
molecular orbitals.

The probability of finding the electrons is more The probability of finding electrons is less in
in the case of bonding molecular orbitals. antibonding molecular orbitals. There is also a node
between the anti-bonding molecular orbital between
two nuclei where the electron density is zero.

These are formed by the combination of + and + These are formed by the overlap of + with – part.
and – with – part of the electron waves

The electron density in the bonding molecular The electron density in the antibonding molecular
orbital in the internuclear region is high. As a orbital in the internuclear region is very low, so the
result, the nuclei are shielded from each other nuclei are directly exposed to each other. Therefore,
and hence the repulsion is very less. the nuclei are less shielded from each other.

The bonding molecular orbitals are represented The corresponding anti-bonding molecular orbitals are
by σ, π, δ. represented by σ∗, π∗, δ∗.

The lowering of the energy of the bonding molecular orbital to the combining atomic orbital is
called stabilization energy, and similarly, an increase in energy of the anti-bonding molecular
orbitals is called destabilization energy.

Crystal Field Theory

The net change in crystal energy resulting from the orientation of d orbitals of a transition metal
cation inside a coordinating group of anions also called ligands.
A major feature of transition metals is their tendency to form complexes. A complex may be
considered as consisting of a central metal atom or ion surrounded by a number of ligands.
The interaction between these ligands with the central metal atom or ion is subject to crystal
field theory.

Crystal field theory was established in 1929 and treats the interaction of metal ion and ligand as a
purely electrostatic phenomenon where the ligands are considered as point charges in the vicinity
of the atomic orbitals of the central atom. Development and extension of crystal field theory
taken into account the partly covalent nature of bonds between the ligand and metal atom mainly
through the application of molecular orbital theory. Crystal field theory is often termed ligand
field theory.

In order to understand clearly the crystal field interactions in transition metal complexes, it is
necessary to have knowledge of the geometrical or spatial disposition of d orbitals. The d-
orbitals are fivefold degenerate in a free gaseous metal ion. If a spherically symmetric field of
negative ligand filed charge is imposed on a central metal ion, the d-orbitals will remain
degenerate but followed by some changes in the energy of the free ion.

Crystal Field Splitting

Crystal field theory was proposed which described the metal-ligand bond as an ionic bond
arising purely from the electrostatic interactions between the metal ions and ligands. Crystal field
theory considers anions as point charges and neutral molecules as dipoles.

When transition metals are not bonded to any ligand, their d orbitals degenerate that is they have
the same energy. When they start bonding with other ligands, due to different symmetries of the
d orbitals and the inductive effect of the ligands on the electrons, the d orbitals split apart and
become non-degenerate.
High Spin and Low Spin

The complexion with the greater number of unpaired electrons is known as the high spin
complex, the low spin complex contains the lesser number of unpaired electrons. High spin
complexes are expected with weak field ligands whereas the crystal field splitting energy is
small Δ. The opposite applies to the low spin complexes in which strong field ligands cause
maximum pairing of electrons in the set of three t2 atomic orbitals due to large Δo.

 High spin – Maximum number of unpaired electrons.

 Low spin – Minimum number of unpaired electrons.
Example: [Co(CN)6]3- & [CoF6]3-

High Spin and Low Spin Complex

 [Co(CN)6]3- – Low spin complex

 [CoF6]3- – High spin complex