COVENANT UNIVERSITY

COLLEGE OF SCIENCE AND TECHNOLOGY

DEPARTMENT OF CHEMISTRY
COURSE TITLE: Basic Inorganic Chemistry
COURSE CODE: CHE212 UNITS: 2
SESSION: 2017/2018 LOCATION: Petroleum Engineering Building C28

BONDING IN COORDINATION CHEMISTRY

Molecular Orbital Theory (Contd.)
Comparison of Bonding Theories
Molecular Orbital Theory
Valence Bond Theory
considers bonds as localized between one pair considers electrons delocalized throughout the
of atoms entire molecule
creates bonds from overlap of atomic orbitals combines atomic orbitals to form molecular
(s, p, d…) and hybrid orbitals (sp, sp2, sp3…) orbitals (σ, σ*, π, π*)
creates bonding and antibonding interactions
forms σ or π bonds
based on which orbitals are filled
predicts molecular shape based on the number predicts the arrangement of electrons in
of regions of electron density molecules
needs multiple structures to describe resonance
VALENCE BOND THEORY
Valence Bond Theory /Pauling’s Theory of Complexes (VBT)
Valence bond theory is one of two commonly used methods in molecular quantum mechanics;
the other is molecular orbital theory. In VBT, a chemical bond is the overlap of two orbitals that
together contain two electrons. The greater the overlap, the stronger the bond and the lower the
energy. When the orbitals overlap along an axis containing the nuclei, they form a σ bond. When
they overlap in a fashion that creates a node along this axis, they form a π bond. This theory
describes bonding using hybrid orbitals and electron pairs, as an extension of the electron-dot
and hybrid orbital methods used for simpler molecules. The valence-bond approach considers
the overlap of the atomic orbitals (AO) of the participation atoms to form a chemical bond: (a
kind of blend or combination of two or more standard atomic orbitals). Due to the overlapping,
electrons are localized in the bond region. According to valence bond theory, electrons reside in
quantum-mechanical orbitals localized on individual atoms. In many cases, these orbitals are
simply the standard s, p, d, and f atomic orbitals. In other cases, these orbitals are hybridized
atomic orbitals, a kind of blend or combination of two or more standard atomic orbitals.
VBT also helps predict the geometry of a four-coordinate d8 complex if its magnetic properties
are known; diamagnetic implies square planar while paramagnetic is tetrahedral.

NOTE
1. If the energy of the system is lowered because of the interactions, then a chemical bond
forms.
2. If the energy of the system is raised by the interactions, then a chemical bond does not
exist.
3. A chemical bond results from the overlap of two half-filled orbitals with spin-pairing
of the two valence electrons (or less commonly the overlap of a completely
4. filled orbital with an empty orbital).
5. The geometry of the overlapping orbitals determines the shape of the molecule.

Hybridization
Combining or mixing the wave functions for the atomic orbital so that they form hybrid orbital is
called hybridization. Hybrid orbital are generated by mixing the characters of atomic orbital. The
reason for creating a set of hybrid orbital is to produce a convenient bonding scheme for a
particular molecular species. The character in the hybrid orbital depends on the atomic orbital
involved and their percentage contributions. The labels given to hybrid orbital reflect the
contributing atomic orbital, e.g. a sp hybrid possesses equal amounts of s and p orbital character.
Hybrid orbitals are still localized on individual atoms, but their shapes and energies differ from
those of standard atomic orbitals.
Hybridization and Geometries
Types of hybridization in metal complexes

Coordination Type of hybridization Geometry Examples

number
2 sp linear [Ag(NH3)2]+
3 sp2 Trigonal planar [HgI3]-
4 sp3 tetrahedral [Ni(CO)4]
4 dsp2 Square planar [Ni(CN)4]2-
5 dsp3 Trigonal bipyramidal [Fe(CO)5
6 d2sp3 octahedral [Co(NH3)6]3+
6 sp3d2 octahedral [CoF6]4-

SP HYBRIDIZATION

This shows formation of two sp hybrid orbital from one 2s atomic orbital and one 2p atomic
orbital. The model of sp hybridization can be used to explain bonding in Beryllium (Be): The
structure of a gaseous molecule of beryllium fluoride BeF2 is linear. Be is the central atom in this
molecule with ground state electronic configuration as shown.

This shows formation of two sp hybrid orbitals from one 2s atomic orbital and one 2p atomic
orbital. Thus, the general rule states that if we begin with n atomic orbital, we must end up with n
orbital after hybridization.

The model of sp hybridization can be used to explain bonding in Beryllium. Other examples are
BeCl2, CO2, and CS2.

The structure of a gaseous molecule of beryllium fluoride BeF2 is linear. Be is the central atom
in this molecule with ground state:
 1s 2s 2p

(b) (a)

Beryllium ground state

1s 2s 2p
Bee

Beryllium excited state

1s 2s 2p

sp hybrid orbitals
sp2 Hybridization

The valence orbitals of a central atom surrounded by three regions of electron density consist of
a set of three sp2 hybrid orbitals and one unhybridized p orbital. This arrangement results from
sp2 hybridization, the mixing of one s orbital and two p orbitals to produce three identical
hybrid orbitals oriented in a trigonal planar geometry.

The final hybrid orbital (sp2) are equivalent in every way except for their directional properties.
The model of sp2 hybridization can be used to describe the σ-bonding in trigonal planar
molecules such as BH3, BF3, and AlCl3 etc.

BF3 molecule

The structure of a boron trifluoride BF3 molecule is a planar triangle with bond angles of 1200.
The B atom is the central atom in the molecule with ground state configuration as shown:
Boron = 1s2, 2s2, 2p1
1s 2s 2p

Boron atom ground state

1s 2s 2p
State

Excited state

1s 2s 2p
State

Sp2

Sp3 hybridization
 Hybridization results as a result of mixing one s and all three p atomic orbitals to produce a set of
four equivalent sp3 hybrid atomic orbitals. When sp3 hybrid orbitals are used for the central atom
in the formation of molecule, the molecule is said to have the shape of a tetrahedron.

The typical molecule is CH4, in which the 1s orbital of H atom overlap with one of the sp3 hybrid
orbitals to form a C-H bond. Four H atoms form four such bonds, and they are all equivalent.
Other molecules and ions having tetrahedral shapes are SiO44-, SO42-.

Example:

TETRAHEDRAL COMPLEXES
[NiCl4]2-
Considering the 4-coordinated complex ion, [NiCl4]2- , the central metal ion in this complex is
Ni2+. To guess the shape of the complex:
i) First find out the number of d electrons. This is arrived at as follows:

No. of d electrons = Atomic no. of central metal – no. of electron lost in ion formation
Atomic no of previous inert gas
Note: This is applicable for the first row transition elements. For the third row Transition
elements, 14 should be subtracted.
ii). Then, these electrons are arranged in the d orbital in such a way that the arrangement
gives no of unpaired electrons which account for the observed magnetic moment.
Iii) From the distribution, available empty orbital is obtained.
iv). Then, for the hybridization, empty metal orbitals equals to its coordination number.
v) Geometry or shape can now be predicted.
For [NiCl4]2- ,
Ni2+ belongs to d8 system
3d 4s 4p 4d
↑↓ ↑↓ ↑↓ ↑ ↑

3d 4s 4p 4d
↑↓ ↑↓ ↑↓ ↑ ↑ : : : :

sp3 hybridisation (tetrahedral complex)

Since the coordination of nickel in this complex is four, the next higher orbitals are required for
hybridization. Hence the geometry of the complex in [NiCl4]2- is tetrahedral. In VB diagram,
arrow (↑) represents metal d electrons and dots (: ) represents electrons donated by igands.
Magnetic moment = √n (n+2) n = 2 (no of unpaired electrons)
= √ 2 (2+2)
=2.83 BM
Class work
No of unpaired electrons Spin-only moment
(BM)
1
2
3
4
5

Class work: predict the geometry and magnetic moment of the complex- [Ni(NH3)4]2+

Tetrahedral (sp3 hybridized) complexes.

Complex [Ni(CO)4 [Zn(NH3)42+ [FeCl4]- [CoCl4]2- [Cu(py)4]+

Magnetic character Diamagnetic diamagnetic Paramagnetic Paramagnetic diamagnetic

(5.92 BM) (3.87)

SQUARE PLANAR COMPLEXES

Another possible geometry for the 4-coordinated complex is the square planar configuration
involving dsp2. For example, [pt(Cl)4]2- (diamagnetic)
[pt(Cl)4]2-
d system = 78-54-2-14 = 8 (d8 system)
The fact that it is diamagnetic clearly indicates that it contains no unpaired electron. These 8
electrons are distributed within 3d level in such a way that there are no unpaired electrons.
3d 4s 4p
Pt2+ in
↑↓ ↑↓ ↑↓ ↑↓
[pt(Cl)4]2-

3d 4s 4p
Pt2+ in
↑↓ ↑↓ ↑↓ ↑↓ : : : :
[pt(Cl)4]

dsp2 hybridization

Class work
Predict the geometry of the complex [Ni(CN)4]2- diamagnetic

Square planar (dsp2 hybridized) complexes

Complex [pt(NH3)4]2+ [ptCl)4]2- [AuCl4]-

Magnetic character Diamagnetic diamagnetic diamagnetic

OCTAHEDRAL COMPLEXES

Predict geometry of the ion [Co(NH3)6]3+ (diamagnetic)

d system = 27-3-18 = 6
Co3+ in
[Co(NH3)6]3+
 3d 4s 4p 4d

↑↓ ↑↓ ↑↓

3d 4s 4p 4d

↑↓ ↑↓ ↑↓ : : : : : :

d2 sp3 hybridization (inner-orbital octahedral complex)

Assignment: Predict the geometry of the complex [CoF6]4- (diamagnetic)

Limitations of Valence Bond Theory

While the VB theory, to a larger extent, explains the formation, structures and magnetic
behaviour of coordination compounds, it suffers from the following shortcomings
(i) It involves a number of assumptions.
(ii) It does not give quantitative interpretation of magnetic data.
(iii) It does not explain the colour exhibited by coordination compounds
(iv) It does not give a quantitative interpretation of the thermodynamic kinetic stabilities
of coordination compounds.
(v) It does not make exact predictions regarding the tetrahedral and square planar
structures of 4-coordinate complexes.
(vi) It does not distinguish between weak and strong ligands.

References

1. Balehausen C. J. and Harry B. Gray Columbia University

2. R. Gopalan and V. Ramalingam, Concise coordination chemistry. VIKAS
publishing house.
3. Olajire Abass. Fundamental University Organic and Inorganic Chemistry. Series
B