Chapter 4 - Valence Bond Theory

Chapter 4:
VALENCE BOND
THEORY
(vbt)
Dr Nur Atiqah Nasir

[email protected]
BONDING IN COORDINATION
COMPOUNDS
• The ligands are bonded to the central atom via the dative
covalent bonding
• Three
theories in explaining the bonding in coordination
compounds:
• Valence Bond Theory (VBT),
• Crystal Field Theory (CFT)
• Molecular Orbital Theory (MOT).
2
MAGNETIC PROPERTIES OF
COMPOUNDS
The magnetic properties of a complex arise from the charge,
spin and electron’s orbital angular momentum
Two types of magnetic properties in a complex:

Diamagnetic – possess by all, closed shell results in
induced magnetic moment opposite to applied magnetic
field, small magnetic effect (ignored)
Paramagnetic – arise from spin and orbital angular

momenta of electron, arise from unpaired electron, large
magnetic effect
• The magnetic properties depends on the number of
unpaired (lone) electrons.
 Electronic spin which cancels the

magnetic field effect.
 Electronic spin which increases the

magnetic field
• In a paramagnetic compounds, the more the unpaired

electrons, the greater the magnetic strength of the
compound.
• In a diamagnetic compounds, there are only paired
electrons and therefore the magnetic strength is small.
MAGNETIC MEASUREMENT
 Magnetic properties can be determined using Gouy’s balance
The value of the magnetic effect is called magnetic moment,  .

The unit is called Bohr Magneton (BM)
 =  [4S (S+1) + L(L+1)];
S = total spin quantum number
L = total orbital angular momentum quantum number
• Since S > L <<<S Ll  =  [4S (S+1) L<<> L;  =  [4S (S+1)]
• For each unpaired e, S =½ and S =Σs,  n = 2S
Remember
• Replacing S with n   =  [n (n + 2)] this
Schematic drawing of Gouy’s Balance
Balance
U S Magnetic Block
Sample
RELATIONSHIP BETWEEN MAGNETIC MOMENT
WITH LONE ELECTRON
0 lone electron,  = 0 = 0 B.M

1 lone electron,  = 3 = 1.73 B.M
2 lone electrons,  = 8 = 2.83 B.M
The unit for magnetic moment is Bohr magneton

(B.M = 9.273 x 10-24 Am2 molecule-1). The value is important in
determining the stereochemistry of the complex.
VALENCE BOND THEORY
 This theory states that the donor atom (ligand) donates a pair
of electrons to the empty orbital of the metal atom to be shared
together (dative or coordinate covalent bond)
For the central metal atom to be bonded, the empty orbitals

should be orientated to a certain direction in the 3D sphere.
The formation of the empty orbital can be explained using the

hybridization theory which includes the s, p and d orbitals of
the metal
FACTS TO SUPPORTS VBT
THEORY
• Three major factors supporting VBT:
Facts from Magnetic Properties of compounds

The usage of hybridization theory.
Relationship with molecular shape.
HYBRIDIZATION, MOLECULAR SHAPE &
COORDINATION NUMBER
Hybrid type Molecule shape Coordination

number
sp Linear 2
sp2 Trigonal 3
sp3 Tetrahedron 4
dsp2 Square planar 4
d2 sp3/sp3d2 Octahedral 6
VBT FOR OCTAHEDRAL
COMPLEXES
Two types of octahedral complexes:
 Internal Orbital Complex (3d24s4p3 = d2sp3)

• Use d orbital with lower n energy rather than n with higher
energy for orbital s and p.
Outer Orbital Complex (4s4p34d2 = sp3d2)

• Use d orbital with higher n energy rather than n with lower
energy for orbital s and p.
INNER OCTAHEDRON
ORBITAL COMPLEXES (d sp )
2 3
• Involve 2 empty d orbitals which has lower energy than s and p

orbitals which is used in the hybridisation
• Complex formed lower spin where the electrons fill in the lower
energy in the d orbital of the metal first
• Magnetic moment value is lower compared to the free metal ion.

• Exists in complexes with metals d , d , d and d
4 5 6 7.
• (Cr(II), Cr(0), Fe(III), Fe(II), Co(III), Co(II) with ligand (CN , CO,
-
NO2) – strong ligand

INNER OCTAHEDRON ORBITAL
COMPLEXES (d2sp3)
• Example I
Hexacyanoferrate(III), [Fe(CN)6]3-
• Coordination No. : 6
• Structure shape : Octahedron
• Magnetic strength: 1.73 (1 lone electron)
• Electronic Config. : d5
INNER OCTAHEDRON ORBITAL
COMPLEXES (d2sp3)
 Example 2
Hexacarbonylchromium, [Cr(CO)6]
 Coordination No. : 6
 Structure shape : Octahedral
 Magnetic strength : 0 (No lone electron)
 Electronic Config : d6 (3d54s1 considered d6)
OUTER ORBITAL OCTAHEDRAL
COMPLEXES (sp3 d2)
• Involve 2 empty d orbitals which has a higher energy than s
and p orbitals which is used in the metal ion hybridisation
• Complex formed higher spin where the electrons fill in the d

orbital of the metal first
• The magnetic moment value is the same compared to the

free metal ion.
• Exists in complexes with metals configuration d1-d10

• Complexes with conf. d4, d5, d6 and d7, the formation depends
on the ligand
OUTER ORBITAL OCTAHEDRAL
COMPLEXES (sp3 d2)
 Example 1
Hexafluorocobalt(III), [CoF6]3-.
 Structure shape : octahedral
 Magnetic strength : 4.89 (4 lone electrons)
 Electronic Config. : d6
MOLECULAR STRUCTURE OF
OCTAHEDRAL COMPLEXES
TETRAHEDRON COMPLEXES (sp3)
• Coordination No. : 4
• Magnetic Property : High spin
• d electron : Fill in all orbital first
• Hybridisation : sp3
• Complex type : All d -d metal complexes except d

1 10 8
with Pt metal ion and other metal

ion with CN- and CO ligands
 Example:
MOLECULAR STRUCTURE OF
TETRAHEDRAL COMPLEXES
SQUARE PLANAR COMPLEXES (dsp2)
 Magnetic Property : Low spin
 d electron : Fill in lower energy orbital first
 Hybridisation : dsp2 (inner orbital complex)
 Complex type : All Pt and d8 complexes with
CN-, NO2, CO ligands
 Example:
MOLECULAR STRUCTURE OF SQUARE
PLANAR COMPLEXES
Spectrochemical Series for Ligands
Ligands that cause a transition metal to have a small crystal
field splitting, which leads to high spin, are called weak-
field ligands.
Ligands that produce a large crystal field splitting, which leads

to low spin, are called strong field ligands.
WEAKNESS OF VBT
• Assume all the five d orbitals having the same energy (degenerate). Even assume 3d
and 4d energy the same.
• Unable to explain the colour/absorbance/electronic spectrum of complexes.
• Does not consider the vast energy difference in the role played by the 3d and 4s
orbitals in bonding.
• Unable to explain in detail the behaviour of the magnetic properties if subject to high
temperature.
• Unable to explain in detail the stereochemistry of complexes eg. the existence of two
different complexes with the same metal ion for example [Fe(H2O)6]2+ (which is
paramagnet,  = 4.89 B.M) and [Fe(CN)6]4- (which is diamagnet,  = 0 B.M)
• Unable to explain the stability of complexes.

Exercise 1
Give a valence bond description of the bonding in each of the following
complexes. Include orbital diagrams for the free metal ion and the metal
ion in the complex. State which hybrid orbitals of the metal ion uses and
the number of unpaired electrons in each complex. Hence determine
the magnetism property and the magnetic moment values of each
complex.
• (i) [Fe(CN) ] 6
3¯
• (ii) [Co(H O) ]
2 6
2+
• (iii) [VCl ]¯
4
• (Given atomic number of Fe = 26, Co = 27, V = 23)

Exercise 2
• You are given two types of complexes [CoBr2Cl2]2- and
[Coen(CN)2] (Co= [Ar] 3d74s2) (Br and Cl are weak ligands
while CN- and en are strong ligands).
Answer all questions below based on these complexes.

• Show the electron filling on the s, p and d-orbitals of a free
atom, free ion and for the complexes.
• Identify the hybridization involves in each complex
• Name the type of complex.
• Calculate the magnetic moment of these complexes.
Exercise 3
Magnetic moment for an octahedron d5 complex [FeF6]3- is 5.9
Bohr Magneton.
• Identify the number of unpaired electron in this complex.

• Draw the orbital diagram for the complex (electron filling).
• State the type of hybridization involves.
• Name the type of complex.
THE END

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Chapter 4:

Dr Nur Atiqah Nasir

Two types of magnetic properties in a complex:

Paramagnetic – arise from spin and orbital angular

 Electronic spin which cancels the

 Electronic spin which increases the

• In a paramagnetic compounds, the more the unpaired

The value of the magnetic effect is called magnetic moment,  .

0 lone electron,  = 0 = 0 B.M

The unit for magnetic moment is Bohr magneton

For the central metal atom to be bonded, the empty orbitals

The formation of the empty orbital can be explained using the

Facts from Magnetic Properties of compounds

Hybrid type Molecule shape Coordination

 Internal Orbital Complex (3d24s4p3 = d2sp3)

Outer Orbital Complex (4s4p34d2 = sp3d2)

• Involve 2 empty d orbitals which has lower energy than s and p

• Magnetic moment value is lower compared to the free metal ion.

NO2) – strong ligand

• Complex formed higher spin where the electrons fill in the d

• The magnetic moment value is the same compared to the

• Exists in complexes with metals configuration d1-d10

• Complex type : All d -d metal complexes except d

with Pt metal ion and other metal

Ligands that produce a large crystal field splitting, which leads

• Unable to explain the colour/absorbance/electronic spectrum of complexes.

• Unable to explain the stability of complexes.

• (Given atomic number of Fe = 26, Co = 27, V = 23)

Answer all questions below based on these complexes.

• Identify the number of unpaired electron in this complex.

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