S.S. JAIN SUBODH P.G.

(AUTONOMOUS) COLLEGE, JAIPUR

MOT with Special Reference to

Octahedral and Tetrahedral Geometry

A SEMINAR
Submitted in
Partial Fulfilment for the degree of
MASTER OF SCIENCE
(CHEMISTRY)
Session 2022-2023

Submi ed to Submi ed by
Dr. Deeksha Sharma Kushagra Gupta
Assistant Professor M.Sc IV Semester
 CERTIFICATE

This is to certify that the seminar entitled

“MOT With Special Reference to
Octahedral and Tetrahedral Geometry” has
been submitted to the Department of
Chemistry, S.S. Jain Subodh P.G.
(Autonomous) College, Jaipur in partial
fulfillment for the degree of Master of Science
(Chemistry).

(Dr. Deeksha Sharma)

Supervisor
 Acknowledgement

I take this opportunity to express a deep sense of

gratitude to Prof. K.B. Sharma Sir Principal and
Management of S.S. Jain P.G. (Autonomous) College,
Jaipur for their cordial support and valuable guidance.

I also take this opportunity to express my profound

gratitude and deep regards to my Supervisor, Dr.
Deeksha Sharma for their exemplary guidance,
monitoring and constant encouragement throughout the
course of this seminar.

Lastly, I thank almighty, my parents and friends for

their constant encouragement without which this
seminar would not be possible.
 Table Of Content

Topic Page No.

1. Introduction 1
2. Octahedral Complexes 2
3. Tetrahedral Complexes 13
4. Square Planner Complexes 16
5. References 19
 MOT With Special Reference to Octahedral and Tetrahedral
Geometry

Introduction

The crystal field theory fails to explain many physical properties of the
transition metal complexes because it does not consider the interaction between the
metal and ligand orbitals. The molecular orbital theory can be very well applied to
transition metal complexes to rationalize the covalent as well as the ionic character in
the metal-ligand bond. A transition metal ion has nine valence atomic orbitals which
are consisted of five nd, three (n+1)p, and one (n+1)s orbitals. These orbitals are of
appropriate energy to form bonding interaction with ligands. The molecular orbital
theory is highly dependent on the geometry of the complex and can successfully be
used for describing octahedral complexes, tetrahedral and square-planar complexes.
The main features of molecular orbital theory for metal complexes are as follows:
1. The atomic orbital of the metal center and of surrounding ligands combine to
form new orbitals, known as molecular orbitals.
2. The number of molecular orbitals formed is the same as that of the number of
atomic orbitals combined.
3. The additive overlap results in the bonding molecular orbital while the
subtractive overlap results in the antibonding overlap.
4. The energy of bonding molecular orbitals is lower than their nonbonding
counterparts while the energy of antibonding molecular orbitals is higher than
that of nonbonding orbitals.
5. The energy of nonbonding orbitals remains the same.
6. The ionic character of the covalent bond arises from the difference in the energy of
combining orbitals.
7. If the energy of a molecular orbital is comparable to an atomic orbital, it will not
be very much different in nature from atomic orbital.
The polarity of the bond can be explained by considering the overlap of two
atomic orbitals of different energies. Suppose ϕA and ϕB are two atomic orbitals of
atoms A and B, respectively. These two atomic orbitals have one electron in each of
them and combine to form one bonding (σ) and one antibonding (σ*) molecular
orbital. After the formation of molecular orbitals, both electrons occupy σ-orbital.
Now, if the energy of σ-orbital is closer to ϕA, it will have more ϕA character and
hence the electron density of both of the electrons will be concentrated more on atom
A than B. Similarly if the energy of σ-orbital is closer to ϕB, it will have more ϕB
character and the electron density of both of the electrons will be concentrated more
on atom B than
A. This same explanation holds for the ionic character in metal-ligand bond.
The main concern here is that the total number of the molecular orbitals
formed as a result of bonding and antibonding interactions is quite large; and
therefore, many complications related to the understanding of symmetry-energy may
arise, all of which needs a very sophisticated treatment of chemical bonding. Hence,
without a comprehensive knowledge of the chemical applications of group theory, it
is quite difficult to explain the whole concept. However, a primitive explanation for
the σ-bonding in transition metal complexes of different geometry can still be give.

Octahedral Complexes
In octahedral complexes, the molecular orbitals created by the coordination of
metal center can be seen as resulting from the donation of two electrons by each of six
σ-donor ligands to the d-orbitals on the metal. The metal orbitals taking part in this type
of bonding are nd, (n+1)p and (n+1)s. It should be noted down that not all nd-orbitals but
only dz2 and d 2 2 orbitals are capable of participating in the σ-overlap. The dxy, dxz and dyz
orbitals remain non-bonding orbitals. The ligands approach the metal center along the x, y
and z-axes in such a way that their σ-symmetry orbitals form bonding and anti-bonding
combinations with metal’s s, px, py, pz, dz2 and d 2 2 orbitals. A total of six bonding and six
anti-bonding molecular orbitals formed. The symmetry designations of different metal
orbitals taking part in octahedral overlap are:
dz2, d−x2 y2 – eg
s – a1g
px, py, pz – t1u
dxy, dxz, dyz – t2g
 The exact nature of the Mulliken symbols, like eg or a1g, etc., can be
understood only after the core level understanding of group theory. However, it still
can be noted that a, e and t represents singly, doubly and triply degenerate orbitals,
respectively. The subscripts g and u represent gerade and ungerade nature of the
orbitals. An orbital is said to be gerade if it has the same sign in all opposite
directions from the center. These are also said to be having the centre of symmetry.
On the other hand, an orbital is said to be ungerade if it has the opposite sign in all the
opposite directions from the center. These are also said to be lacking the centre of
symmetry.
The symmetry adapted linear combinations of atomic orbitals (SALCs) for
metal-ligand direct overlap can be obtained just by resolving the reducible
representation based on the bond vectors along the axis of σ-overlap. As there are
total six bond vectors for the metal-ligand σ-bonding, hexa-dimensional reducible
representation will be obtained. As the six ligands in an octahedral complex approach
the central metal ion along the three Cartesian axes (two along x-axis, two along
y-axis and two along z-axis), the six σ-basis bond vectors must also be selected along
x, y and z-axis.
 Figure 3. The octahedral coordination and corresponding σ-basis set
for ligand orbitals in octahedral complexes.

The symmetry adapted linear combinations of these fall into three irreducible
representations labeled as a1g, eg, and t1u. The symmetry designations of different
ligand orbitals taking part in octahedral overlap are:

Table 1. Reducible representation based on bond vectors in the octahedral

geometry.
O E 8C 6C 6C 3C i 6S 8S 3σ 6σ Irreduci
h 3 2 4 2 4 6 h d
ble
compone
nts
Γπ 6 0 0 2 2 0 0 0 4 2 a1g + eg + t1u

The metal-orbital sets of a1g, eg and t1u symmetry participate in σ-bonding by

interacting with the same symmetry SALCs sets to produce σ-bonding and
antibonding molecular orbitals. However, the triply degenerate t2g orbitals set on the
metal remains nonbonding as there no ligand orbitals of this symmetry. The exact
nature of the “symmetry adapted linear combination of atomic orbitals” or simply
SALCs is quite complex and is beyond the scope of this volume but still we can
simply give a superficial explanation for these ligand orbitals. The pictorial
representation of various SALC orbitals in octahedral complexes, capable of σ-
overlap with metal orbitals, can be given as:

1. If the six atomic orbitals of six ligands are pointing their positive lobes towards
metal’s s-orbital, then the composite orbital becomes:

φ1 = σ1 + σ2 + σ3 + σ4 + σ5 + σ6 (1)

The pictorial representation is given below.

Figure 4. The combination of ligand orbitals overlapping with s-orbital

of the metal center.

2. The px-orbital of metal center can overlap with ligands atomic orbital approaching
along the x-axis. Hence, the composite orbital becomes:

φ2 = σ1 – σ2 (2)
The pictorial representation is given below.

Figure 5. The combination of ligand orbitals overlapping with px-orbital

of the metal center.

3. The py-orbital of metal center can overlap with ligands atomic orbital approaching
along y-axis. Hence, the composite orbital becomes:

φ3 = σ3 – σ4 (3)

The pictorial representation is given below.

Figure 6. The combination of ligand orbitals overlapping with py-orbital

of the metal center.
4. The pz-orbital of metal center can overlap with ligands atomic orbital approaching
along z-axis. Hence, the composite orbital becomes:

φ4 = σ5 – σ6 (4)

The pictorial representation is given below.

Figure 7. The combination of ligand orbitals overlapping with pz-orbital

of the metal center.

5. The d 2 2 orbital of metal center can overlap with ligands atomic orbital
approaching along x and y-axis. Hence, the composite orbital becomes:

φ5 = σ1 + σ2 – σ3 – σ4 (5)
The pictorial representation is given below.

Figure 8. The combination of ligand orbitals overlapping with dx2 y2 orbital

of the metal center. –

6. The dz2 orbital of metal center can overlap with ligands atomic orbital approaching
along x, y and z-axis. Hence, the composite orbital becomes:

φ6 = σ5 + σ6 – σ1 – σ2 – σ3 – σ4 (6)

The pictorial representation is given below.

Figure 9. The combination of ligand orbitals overlapping with dz2 orbital

of the metal center.
The overall molecular orbital energy level diagram for σ-bonding in octahedral
complexes can be shown as:

Figure 10. The formation of σ-molecular orbitals (bonding, antibonding

and non-bonding) in octahedral complexes of transition metals.
 The φ1 composite orbital of a1g symmetry interacts with a1g orbital set of metal
ions and produces one bonding (a1g) and one antibonding molecular orbital (a* ). The
φ2, φ3 and φ4 composite orbital set of t1u symmetry interacts with t1u orbital set of
metal ions and produces triply-degenerate bonding (t1u) and triply- degenerate
antibonding molecular orbital (t* ) set. The φ and φ composite orbital set of e
symmetry interacts with eg orbital set of metal ions and produces doubly-degenerate
bonding (eg) and doubly-degenerate antibonding molecular orbital (e* ) set. The t
orbital set of the metal center remains non-bonding in nature. The electron-filling in
various orbitals is done in accordance with the Aufbau principle, Hund’s rule and
Pauli exclusion principle.
Some typical explanations in the view of MO-theory are:

i) Spin only magnetic moments: Just like crystal field theory, MO-theory can also
be used to rationalize the spin only magnetic moments of different transition metal
complexes. For instance, 5.9 B.M. magnetic moment of [Mn(H2O)6]2+ is generated
when seventeen electrons (five from Mn2+ and twelve electrons from six aquo
ligands) are filled in different molecular orbitals. Twelve out of seventeen electrons
occupy six bonding molecular orbitals of a1g, t1u and eg. Three out of the remaining
five electrons are filled in nonbonding t2g and the last two electrons occupy e* giving
a total of five unpaired electrons.

ii) 18- electron rule: It is a well-known fact that metal carbonyls and many other
complexes follow 18-electron rule quite well. This is also analyzed in terms of
effective atomic number which suggests that a total of 18- electrons in the valence
shell generally makes overall electron-count to resemble a noble gas core. However, a
strong basis for this rule can found in molecular orbital theory. Six bonding molecular
orbitals can accommodate a total of 12 electrons and only six electrons can be filled
in the non-bonding t2g. Any extra
electron is bound to occupy the antibonding e* orbital and hence affects the stability.
iii) The splitting of d-orbital: According to crystal field theory, the splitting, Δo of
d-orbital in t2g and eg is produced by the difference in the Coulombic repulsion
experienced various metal orbitals. However, the molecular orbital theory sees the
splitting of d-orbital as a result of the interaction of metal orbitals with ligand orbitals
and labels it as splitting between nonbonding t2g and antibonding e*.

iv) High spin – low spin complexes: Just like in the case of crystal field theory, the
magnitude of Δo decides
the multiplicity nature of the complexes. If the separation between nonbonding t2g and
antibonding e* is pretty
large, the electrons prefer to pair up with the electrons already present in nonbonding t2g
and the complex becomes low-spin. On the other side, If the separation between
nonbonding t2g and antibonding e* is small,
the electrons prefer to occupy antibonding e* and the complex becomes high-spin. For
example, in
[Co(NH3)6]3+, the magnitude of Δo is very large and the configuration becomes t 6, e* 0.
Furthermore, the
comparatively lower stability and weaker metal-ligand bond in high spin complexes
may be attributed to the presence of electrons in a molecular orbital of antibonding
nature.

v) Jahn-Teller distortions: The concept of molecular orbital theory can also be used
to rationalize the z-out or z-in distortion of the octahedral metal complexes. For
example, octahedral complexes of Cu2+ ion have been known to undergo Jahn-Teller
distortion due to d9 configuration. According to molecular orbital theory, the
electronic configuration octahedral complexes of Cu2+ will be t 6, e* 3. Now, as the
energy of e * molecular orbital is close to the pure atomic orbitals of metal ion, eg*
would resemble more to the metal orbitals than the ligand’s. Therefore, we can
approximate eg* to pure dx2–y2 and dz2. Now if the configuration is (dx2–y2)1 (dz2)2,
higher antibonding electron density along z-axis would result in a weaker bond and an
elongation of bonds would take place along z-axis, giving a z-out distortion. On the
other hand, if the configuration is (dx2–y2)2 (dz2)1, higher antibonding electron density
along x and y-axis would result in a weaker bond and an elongation would take place
along x and y-axis, giving a z-in distortion.

vi) Variation of ionic radii: Experimental values of ionic radii of central metal ions
in bivalent salts of first transition series were very well explained by the crystal field
theory. The same can be done in the frame of molecular orbital theory. The decrease
in ionic radii, when one moves from Ca2+ to V2+, may be attributed to the increasing
magnitude of effective nuclear charge while the filling of valence electrons takes
place in nonbonding t2g. However, after V2+, the fourth electron in Cr2+ is filled in
antibonding e* and this effect makes the metal-ligand bond to increase, which in turn
results in an increment in effective ionic radius. This trend continues up to Mn2+, but
as we move from Fe2+ to Ni2+, the electron filling again goes to nonbonding t2g and
thus thereby decreases the ionic radii. The ninth and tenth electron in Cu2+ and Zn2+
are filled in antibonding e* and therefore, the effective ionic radius increases again.
The whole situation creates two minima in effective ionic radii, one for V2+ and other
for Ni2+.
It is worth to note down that the more sophisticated rationalization of the
MO-diagram for octahedral complexes can be given in the terms of molecular
symmetry combined with detailed quantum mechanics involved. In general practice,
six symmetry-adapted linear combinations (SALCs) of atomic orbitals, corresponding
to the irreducible components of the bond-vector based reducible representation, are
created. The irreducible representations that these SALCs span to are a1g, t1u and eg.
The metal also has six valence orbitals that span the same irreducible representations
(s-orbital is labeled as a1g, a set of three p-orbitals is labeled t1u, and the dz2 and dx2−y2
orbitals are labeled eg). The six σ-bonding molecular orbitals result from the
combinations of ligand SALC's with metal orbitals of the same symmetry.
Tetrahedral Complexes
In tetrahedral complexes, the molecular orbitals created by the coordination
profile can be seen as resulting from the donation of one electron pair by each of four
σ-donor ligands to the d-orbitals on the transition metal. The visualization of the
composite orbital of a tetrahedral complex in the molecular orbital framework is quite
difficult because of the absence of the centre of symmetry. However, the symmetry
designations of different metal orbitals taking part in this type of overlap can still be
given as:

s – a1
px, py, pz – t2
dxy, dxz, dyz – t2
dz2, d−x2 y2 – e

The symmetry adapted linear combinations of atomic orbitals (SALCs) for

metal-ligand direct overlap can be obtained just by resolving the reducible
representation based on the bond vectors along the axis of σ-overlap. As there is a
total of four bond vectors for the metal-ligand σ-bonding, the four-dimensional
reducible representation will be obtained.
 Figure 11. The σ-basis set for ligand orbitals in
tetrahedral complexes.

The symmetry adapted linear combinations of these fall into two (one singly and one
triply degenerate) irreducible representations labeled as a1 and t2. The symmetry
designations of different ligand orbitals taking part in tetrahedral overlap are:

Table 2. Reducible representation based on perpendicular vectors in a

tetrahedral geometry.
Td E 8C 3C 6S 6σ Irreducible
3 2 4 d components
Γπ 4 1 0 0 2 a1 + t2

The dxy, dxz and dyz orbitals set on the metal also have t2-symmetry. Similarly,
the px, py and pz-orbital set of the metal also has t2 symmetry which resembles with
the symmetry of one of SALCs set on ligands. Therefore, these same-symmetry (t2)
sets from metal and ligand interact to create three bonding and antibonding molecular
orbitals. Moreover, s-orbital on metal has a1-symmetry and hence mix-up with one of
ligand SALC with a1-symmetry. This also results in one bonding and one antibonding
molecular orbital. One metal-orbital set of a1 symmetry and two sets of t2 symmetry
participate in σ-bonding while the doubly degenerate e-symmetry set remains
nonbonding. The overall molecular orbital energy level diagram for σ- bonding in
tetrahedral complexes can be shown as:

Figure 12. The formation of σ-molecular orbitals (bonding, antibonding and

non-bonding) in tetrahedral complexes of transition metals.
Square Planner Complexes
In square-planar complexes, the molecular orbitals created by coordination can be
seen as resulting from the donation of two electrons by each of four σ-donor ligands to the
d-orbitals on the metal. The metal orbitals taking part in this type of bonding are nd,
(n+1)p and (n+1)s. It should be noted down that not all nd or (n+1)p orbitals but only dz2,
d 2 2, px and py-orbitals are capable of participating in the σ-overlap. The dxy, dxz, dyz and
pz-orbitals remain non-bonding orbitals. The symmetry designations of different metal
orbitals taking part in square-planar overlap are:

s – a1g
px, py – eu
dz2 – a1g
dx2−y2 – b1g
pz – a2u
dxy – b2g
dyz, – eg
dxz

The symmetry adapted linear combinations of ligand atomic orbitals (SALCs)

for metal-ligand sidewise overlap in square planar complexes can be obtained just by
resolving the reducible representation based on the bond vectors along to the axis of
σ-overlap. As there are total four bond vectors for the metal- ligand σ-bonding, the
four-dimensional reducible representation will be obtained.
 Figure 13. The σ-basis set for ligand orbitals and corresponding coordination
in square-planar complexes of transition metals.

The symmetry adapted linear combinations of these fall into three irreducible
representations labeled as a1g, b1g and eu. The symmetry designations of different
ligand SALC-orbitals taking part in square-planar overlap are:
Table 3. Reducible representation based on perpendicular vectors in square planner
geometry.
’ ’’
D4 E 2C C2 2C2 2C2 i 2S σ 2σ 2σ Irreducib
h 4 4 h v d
le
compone
nts
Γπ 4 0 0 2 0 0 0 4 2 0 a1g + b1g + eu

The irreducible components that these SALCs span to are a1g, b1g and eu. The
molecular orbitals of σ- bonding in square-planar complexes result from the mixing of
ligand SALCs with metal orbitals of the same symmetry. Two metal-orbital sets of a1g
symmetry, one set of b1g symmetry and one set on eu symmetry participate in
σ-bonding while the doubly degenerate eg and singly degenerate b2g sets remain
nonbonding. This is quite logical because there are no ligand orbitals with these
symmetry properties and hence no orbital overlap is possible. The ligands approach
the metal center along the x and y-axes in such a way that their σ- symmetry orbitals
form bonding and anti-bonding combinations with metal’s s, px, py, dz2 and dx2−y2
orbitals. Two a1g-symmetry sets of metal orbitals (s and dz2) interact with the ligands
SALC of the same symmetry and form three molecular orbitals. The b1g-symmetry set
of metal orbital (dx2−y2) interact with the ligands SALC of same symmetry and form
two molecular orbitals, one bonding and one of antibonding nature.
Similarly, eu-symmetry set of metal orbitals (px, py) interacts with the ligands
SALC of the same symmetry and form bonding and antibonding molecular orbital
sets. A total of nine sets of molecular orbitals are formed in which electron filling has
to occur. Furthermore, it should also be noted that bonding molecular orbitals are
predominantly associated with ligands which can be attributed to the lower energy of
ligand SALCs while the antibonding molecular orbitals are primarily associated with
the metal center owing to the higher energy of its atomic orbitals. In other words, the
simplistic approach can treat bonding molecular orbitals as ligand orbitals and
antibonding molecular orbitals as metal orbitals.
References:
1. Descriptive Inorganic, Coordination and Solid-State Chemistry By GLEN E.
RODGERS
2. Principles of Structure and Reactivity By JAMES E. HUHEEY
3. Inorganic Chemistry 4th edition By CATHERINE E. HOUSE CROFT AND
ALAN G. SHARPE
4. Chem Academy Pvt. Ltd. Jaipur.