CHE212

SELECTED TOPICS IN CHEMISTRY FOR CHEMICAL ENGINEERING 1

BY
DR. A. A. AKINSIKU

CHEMISTRY DEPARTMENT
COLLEGE OF SCIENCE & TECHNOLOGY

1
 BONDING IN COORDINATION
CHEMISTRY

(VBT & CFSE calculation)

2
Valence Bond Theory (Contd.)
• useful in predicting some of the chemical and
physical properties of complexes
• failed to explain some facts
• chemical bond is the overlap of atomic orbitals
that together contain two electrons.
• The greater the overlap; the stronger the bond
and the lower the energy.

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• When orbitals overlap • When orbitals overlap in
along an axis a fashion that creates a
containing the nuclei, node along this axis,
they form a σ bond they form a π bond.

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• Extension of the electron-dot and hybrid orbital
methods used for simpler molecules.
• Description of bonding using hybrid orbitals and
electron pairs
• Due to the overlapping, electrons are localized in
the bond region.
• electrons reside in quantum-mechanical orbitals
localized on individual atoms.
• these orbitals are simply the standard s, p, d, and
f atomic orbitals.

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Hybridization
• Combining or mixing the wave functions for the
atomic orbital to form hybrid orbital
• Hybrid orbital are generated by mixing the
characters of atomic orbital.
• Character in the hybrid orbital depends on the
atomic orbital involved and their percentage
contributions.
• 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. 6
Hybrid Orbitals and Geometries

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LIGANDS
• Lewis bases coordinated or bonded to a metal ion
in coordination complex.
• They are electron-pair donors
• ligands may be neutral molecules (e.g. H2O, NH3
or CO)
• Anions (e.g. CN-, Cl- etc.) that have at least one
atom with a lone pair of electrons for donation
to the central metal atom.
• ligand is nucleophilic
TYPES OF LIGANDS
Anionic Monodentate Ligands
F- Fluoro OH- Hydroxo
Cl- Chloro SO42- Sulfato
Br- Bromo S2O32- Thiosulfato
I- Iodo NO2- Nitrito-N-; Nitro
O2- Oxo ONO- Nitrito-O-; Nitrito
CN- Cyano SCN- Thiocyanato-S-;
Thiocyanato

NC- Isocyano NCS- Thiocyanato-N-;

Isothiocyanao
Neutral Monodentate Ligands

NH3 Ammine

H2O Aqua

CO Carbonyl

NO Nitrosyl

CH3NH2 Methylamine

C5H5N Pyridine
• Ligands: Lewis bases
• Transition metal ion: Lewis acid
• Co(NH3)63+
• Pt(NH3)3Br+
Coordination
number Type of hybridization
Geometry
2 sp linear
3 sp2 Trigonal planar
4 sp3 tetrahedral
4 dsp2 Square planar
5 dsp3 Trigonal bipyramidal
6 d2sp3 octahedral
6 sp3d2 octahedral

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SP HYBRIDIZATION
• formation of two sp hybrid orbital from one 2s
atomic orbital and one 2p atomic orbital.
• For example;
• Structure of a gaseous molecule of beryllium
fluoride BeF2 is linear.
• Be is the central atom in this molecule with
ground state:

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14
• This shows formation of two sp hybrid orbitals
from one 2s atomic orbital and one 2p atomic
orbital.

• 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 BeCl , CO , and CS . 15
sp2 Hybridization
• 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.
• Model of sp2 hybridization can be used to describe
the σ-bonding in trigonal planar molecules such as
BH3, BF3, and AlCl3 etc.
For example; BF3 molecule
• structure is a planar triangle
• The B atom is the central atom in the molecule
with ground state configuration as shown:
Boron = 1s2, 2s2, 2p1
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sp3 hybridization
• one s + all three p atomic orbitals =
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.
• 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-. 19
Example:
TETRAHEDRAL COMPLEXES
[NiCl4]2-
Considering the 4-coordinated complex ion,
• [NiCl4]2- is a 4-coordinated complex ion
• central metal ion in this complex is Ni
To guess the shape of the complex:
1. First find out the number of d electrons.

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. 20
For the third row Transition elements, 14 should be
subtracted.
2. Arrange electrons in the d orbital in such a way that
the arrangement gives no of unpaired electrons which
account for the observed magnetic moment.
3. From the distribution, available empty orbital is
obtained.
4. For the hybridization, empty metal orbitals equals
to its coordination number.
5. Geometry or shape can now be predicted.

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 For [NiCl4]2- ,
Ni2+ belongs to d8 system

3d 4s 4p 4d
↑↓ ↑↓ ↑↓ ↑ ↑

3d 4s 4p 4d
↑↓ ↑↓ ↑↓ ↑ ↑ : : : :

sp3 hybridisation (tetrahedral complex)

arrow (↑) = metal d electrons

dots (: ) = electrons donated by ligands 22
• 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 ligands.
Magnetic moment = √n (n+2)
n = 2 (no of unpaired electrons)
= √ 2 (2+2)
=2.83 BM
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Class work
No of unpaired electrons Spin-only moment
(BM)
1
2
3
4
5 24
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.

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 3d 4s 4p
Pt2+ in
2- ↑↓ ↑↓ ↑↓ ↑↓
[pt(Cl)4]

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

dsp2 hybridization

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OCTAHEDRAL COMPLEXES
Predict geometry of the ion [Co(NH3)6]3+ (diamagnetic)
d system = 27-3-18 = 6
Co3+ in [Co(NH3)6]3+

Assignment: Predict the geometry of the complex

[CoF6]3- (diamagnetic) 29
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Limitations of Valence Bond Theory
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.
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(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.

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ASSIGNMENT
Write a term paper on
Groups IA and IIA

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References
1. C. J. BALEHAUSEN and HARRY B. GRAY Columbia
University
2. Olajire Abass. Fundamental University Organics
and Inorganic Chemistry. Series B
3. R. Gopalan and V. Ramalingam, Concise
coordination chemistry. VIKAS publishing house.

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Crystal Field Theory
• Focus: energies of the d orbitals

• Assumptions
• 1. Ligands: negative point charges
• 2. Metal-ligand bonding: entirely ionic

• strong-field (low-spin): large splitting of d orbitals,

electron
pairing
• weak-field (high-spin): small splitting of d orbitals
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CRYSTAL FIELD THEORY
• initiated in 1929 by the German born US Physicist
Hans Albrecht Bethe (1906) and extensively
developed in the 1930s.
• coordinate bond is assumed to consist entirely of
the electrostatic attraction between the positively
charged cation and a ligand.
• The elastatic field produced by the ligands splits
the degenerate the orbitals of the metals.
• describes the breaking of orbital degeneracy in
transition metal complexes due to the presence
of ligands.
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• CFT qualitatively describes the strength of the
metal-ligand bonds.
• Based on the strength of the metal-ligand bonds,
the energy of the system is altered. This may lead
to a change in magnetic properties as well
as colour.
• VBT is used to interpret the spectra of complexes of
the d-block elements.
• The theory considers the metal ion being placed in
an electrostatic field created by the surrounding
molecules or ions.
• The electric field changes the energies of the d
electrons in the case of transition metal ions. 38
The two types of d-orbitals and function are summarized
SN Types of d-orbitals Function
1 dx2-y2 and dz2 Have lobes lying along the mutually perpendicular x, y
and z axes
2 dxy, dy2 and dx2 Have lobes point between the axes

Shapes of d orbitals
The five 3d orbitals are:
3dxy, 3dxz, 3dyz, 3dx² - y², 3dz²

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CRYSTAL FIELD STABILIZATION ENERGY (CFSE)

Splitting of d orbitals in Tetrahedral Complexes

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• splitting observed in a tetrahedral crystal field is
the opposite of the splitting in an octahedral
complex.
• Because a tetrahedral complex has fewer ligands,
the magnitude of the splitting is smaller.
• The difference between the energies of the t2g
• and eg orbitals in a tetrahedral complex ( t) is
slightly less than half as large as the splitting in
analogous octahedral complexes ( o).
t < o, ( t˷ 4/9 o)
• Under influence of ligands in tetrahedral
complexes, the order of increasing energy of
various d orbitals is; dxz = dyz < dxy < dz2 < dx2-y2 42
Splitting of d orbitals in Square Planar Complexes

The order of increasing energy of various d orbitals

is; dxz = dyz < dz2< dxy < dx2-y2
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 High-Spin Versus Low-Spin Octahedral
Complexes
• Degenerate orbitals are filled according to
Hund's rules.
• One electron is added to each of the
degenerate orbitals in a subshell before a
second electron is added to any orbital in the
subshell.
• Electrons are added to a subshell with the
same value of the spin quantum number
until each orbital in the subshell has at least
one electron. 46
High spin Low spin 47
48
49
 The Spectrochemical Series

Note

When geometry and the ligands are held constant, this splitting decreases in the following
order.
Pt4+ > Ir3+ > Rh3+ > Co3+ > Cr3+ > Fe3+ > Fe2+ > Co2+ > Ni2+ > Mn2+

strong-field ligands (low spin) weak-field ligands

1. Metal ions at one end of this continuum are called strong-field ions, because the
splitting due to the crystal field is unusually strong.
2. Ions at the other end are known as weak-field ions. When the geometry and the
metal are held constant, the splitting of the d orbitals decreases in the following
order.

CO > CN- > NO2- > NH3 > -NCS- > H2O > OH- F- -SCN- > Cl- > Br-

strong-field ligands weak-field ligands

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NOTE
The splitting of d orbitals in the crystal field
model depends on the following:
•Geometry of the complex,
•Nature of the metal ion,
•The charge on this ion, and
•Ligands that surround the metal.

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 d1
_ _
↑ _ _

(t2g)1 (eg)0

CFSE = (-0.4 x1) + (0.6 x 0) = -0.4∆o

t2g eg

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Octahedral transition-metal ions with
d1, d2, or d3 are described by the following
diagrams.

CCCCalculate CFSE, for each of the above

d orbital splitting.

Hint: d1 = -0.4∆ , d2 = -0.8 ∆ , d3 = -1.2 ∆ 53

• to add a fourth electron, there is a
problem.
• This electron could be used to pair one of
the electrons in the lower energy (t2g) set of
orbitals or it could be placed in one of the
higher energy (eg) orbitals.

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• One of these configurations is called high-
spin because it contains four unpaired
electrons with the same spin.

• The other is called low-spin because it

contains only two unpaired electrons.

• The same problem occurs with octahedral

d5,d6, and d7 complexes.

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NOTE
• For d1, d2, d3 , d8, d9, and d10 systems in
octahedral complexes, there is only one
ground state for each of the system
obtained. on the basis of the fact that these
electrons will occupy the lowest-energy
state possible.
• All the other remaining systems, d4, d5, d6
and d7 possess two states, namely; high-
spin (spin-free or weak field) and low spin
(spin paired or strong field).
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For octahedral d8, d9, andd10 complexes,
there is only one way to write satisfactory
configurations.

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 d8
↑ ↑
↑↓ ↑↓ ↑↓

(t2g)6 (eg)2
CFSE = (-0.4 x6) + (0.6 x 2) = -1.2 ∆o

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High-spin complexes are expected among
metal ions and ligands that lie toward the low-
field end of these series.

d5 d5
↑ ↑ - -
↑ ↑ ↑ ↑↓ ↑↓ ↑

high-spin (spin free) For Low-spin (spin paired)

5 unpaired electrons 0 unpaired electrons
(t2g)3 (eg)2 (t2g)5 (eg)0 CFSE = (-0.4 x5) + (0) = -2.0 + 2Ep

CFSE = (-0.4 x3) + (0.6 x 2) = 0

(Ep = electron pairing energy) 60

Practice Problem
1. Explain why the Co(NH3)63+ ion is a diamagnetic,
low-spin complex, whereas the CoF63- ion is a
paramagnetic, high-spin complex.
2. What do you understand by Jahn-Teller
Distortion

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62
Tutorial Questions
1. Show the structure of the eg and t2g orbitals
2. Explain the effect of the interactions of the
following on the ligand field of metal
complexes
(a) Sigma donor ligand (b) pie donor ligand
and (c) pie acceptor ligand
(b) Briefly discuss and show the ternary
structures of the following oxides
➢ Fe3O4
➢ Co3O4
➢ Mn3O4 63