CML 100 Inorganic Chemistry Component

Instructor: Prof. Kuntal Manna Room: MS 720: Tel 1510

Coordination Chemistry Organometallic Chemistry Bio inorganic Chemistry

Crystal field theory, Crystal Field The 18 electron rule, Metal Role of transition metals such as
Stabilization Energy, Explaining Carbonyls , Unique reactions of Fe and Zn in biological systems,
physical properties, magnetic organometallics and their use in Cytochromes, Myoglobin,
properties, distortion of shape homogeneous catalysis Hemoglobin, and Carbonic
and color of complexes using CFT anhydrase

• 13 Lectures
• 4 Tutorials
• Lecture slides will be available
as pdf files

1
 Text books for Inorganic Chemistry Part

J. E. Huheey B.D.Gupta
Keiter & Keiter A. J. Elias

Copies available in the textbook section of library

2
How & Why?

3
 How & Why?
Color of metal complexes
Distortion in the shape of complexes

Magnetic properties of complexes

4
Theories of Bonding in transition metal complexes
Theories of bonding were proposed and used to explain the observed properties of transition
metal complexes such as color, magnetism, shape of complexes

Valence bond theory

Linus Pauling
Nobel 1954,1962

Crystal Field theory

Hans Bethe
Nobel 1967
Molecular Orbital Theory

Mulliken (Nobel
5
1966) & Hund
 Theories of bonding in transition metal complexes – in a nutshell
to explain the observed properties of the metal complexes such as color, magnetism, shape

Valence bond theory

• Based on the concept of hybridization sp3, dsp2, dsp3, d2sp3 & sp3d2 : Predicts
shapes of complexes very efficiently
• Can determine magnetic moment if hybridization is known and vice versa
• Does not explain color of complexes, distortion of shape of complexes
• Does not predict strength of ligands or temperature dependence of magnetic
moments
Linus Pauling
Crystal Field theory
•Basic assumptions: Ligands and metal are point charges and the attraction
between them is purely electrostatic in nature
•Considers how the energies of the five metal d orbitals change in the
presence of a ligand field (removing /lifting of the degeneracy).
•Provides explanation to color, arranges ligands according to their strength, Ajoy Ghatak
Hans Bethe
explains distortion of complexes and anomalies in their physical properties
•VBT and CFT should not be MIXED: A common mistake done by many students

Molecular Orbital Theory

•A larger picture where both metal orbitals and ligand group orbitals are
made to form bonding, non bonding and antibonding orbitals.
• CFT splitting is included in this picture; also orbital overlap: π bonding Mulliken & Hund
6
•Explains color, magnetism and energetics (does not predict shape)
Tetrahedral e.g. [Zn(OH)4]2- Square Planar e.g. [Ni(CN)4]2-

Limitations of VB theory
Cannot account for colour of complexes
May predict magnetism wrongly
Cannot account for spectrochemical series

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Background requirement: +2 level CBSE/ICSE and JEE advanced syllabus level

NCERT CHEMISTRY Class 12 Textbook Book 1 8

NCERT CHEMISTRY Class 12 Textbook Book 1 9
 Finding an explanation for the observed properties of transition metal complexes
using Crytal Field Theory

Variation of some physical properties Magnetic properties of complexes

of metal complexes across a period

Temperature dependence of magnetic moments

Distortion in the shape of complexes Color of metal complexes

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 Energetics involved in the CFT model
Basic Assumptions of Crystal Field theory ( concept borrowed from solid state physics)

•The ligands and the metal are considered as point charges

•The attraction between the metal and the ligands is purely electrostatic
•Properties of the metal complexes are explained based on changes happening to the d
orbitals of the metal only

i) Separated metal and ligands at

high energy i
ii) Electrostatic attraction between
metal and ligands leading to
stabilization (heart of CFT)
iii) Destabilization due to ligand
iv
iii
electrons- metal d electrons
repulsion in a spherical field
iv) Further splitting of the 5 d orbitals ii
to 2 sets due to an octahedral field.
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d-orbitals: look attentively along the axis
Linear combination of
dz2-dx2 and dz2-dy2

d2z2-x2-y2
Orbitals affected when ligands approach a metal in an octahedral arrangement

Ligands with their pair of

electrons approach the
metal along the X, Y and Z
axes for an octahedral
complex formation

d-orbitals having lobes pointing directly at x,y and

z axis are repelled most by electron-electron
repulsion

d-orbitals not pointing directly at x, y and z axis are

stabilized to maintain the overall energy same13
 Splitting of the d-orbitals in an octahedral field
d - orbitals splitting in an
octahedral crystal field
eg

d - orbitals in a spherical d x2 – y2 d z2
field of six ligands
+0.6o
o or
Energy

10Dq
-0.4o
d - orbitals stabilized
by metal- ligand
electrostatic attraction
d xy d yz d xz

t2g

t2g : triply degenerate set of orbitals :

eg doubly degenerate set of orbitals
g= gerade: symmetric with respect to the centre of inversion
u= ungerade : antisymmetric w. r. t the centre of inversion
Barycenter: A point between objects where
they balance each other
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 High Spin Vs. Low Spin (d1 to d10)
When does a complex prefer High Spin/ low spin arrangement of electrons?

o < Pairing energy : High Spin o > Pairing Energy : Low Spin

o P
[Fe(H2O)6 ]2+ d6 9350 19150 High Spin o < P
15
[Fe(CN)6 ]4- d6 32200 19150 Low Spin o > P
 Crystal Field Stabilization Energy : The d4 Case

Weak Field/ High Spin Strong Field/Low Spin

o > P
o < P
eg

eg

+0.6o
Energy

+0.6o

-0.4o -0.4o

t2g

t2g

t2g3eg1 t2g4eg0

CFSE = -1.2 o + 0.6o CFSE = -1.6 o + 1 pairing

= - 0.6 o = - 1.6 o + P
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 What is Pairing Energy, P?

The pairing energy is not an experimentally obtained value like o and is

same for a metal ion irrespective of the ligands. It is made up of two
terms.
1) The inherent coulombic repulsion that must be overcome when two
electrons are forced to occupy the same orbital. (Destabilizing energy
contribution of Pc for each doubly occupied orbital).
2) Loss of exchange energy ( based on Hunds rule) that occurs as two
electrons with parallel spin () are forced to become antiparrallel ()
in an orbital. (contribution of Pe for each pair having same spin and same
energy)

P = sum of all Pc and Pe interactions

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The d5 and d6 low spin cases and the correct way to determine
pairing energy contribution

+0.6o +0.6o

-0.4o -0.4o

CFSE = -2.0o +2P CFSE = -2.4o +2P

CFSE = -2.4o +3P

Always compare the extent of pairing with the situation before the splitting of
five d orbitals occurred
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 The crystal field stabilization energy (CFSE)
The stability that results from placing a transition metal ion in the
crystal field generated by a set of ligands.

It arises due to the fact that when the d-orbitals are split in a ligand
field, some of them become lower in energy than before with
respect to a spherical field in which all five d-orbitals were
degenerate.

For example, in an octahedral case, the t2g set becomes lower in

energy with respect to the barycenter. As a result, if there are any
electrons occupying these t2gorbitals, the metal ion is more stable
in the ligand field relative to the barycenter by an amount known
as the CFSE.

Conversely, the eg orbitals (in the octahedral case) are higher in

energy with respect to the barycenter, so having electrons in these
orbitals reduces the amount of CFSE.
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 dn Mag moment Elec. Config. CFSE
d1 1.73 BM t2g1 -0.4 o
d2 2.83 BM t2g2 -0.8 o
d3 3.87 BM t2g3 -1.2 o
d4 4.90 BM t2g3 eg1 -0.6 o
d4 LS 2.83 BM t2g4 -1.6 o +P
d5 5.92 BM t2g3 eg2 0
d5 LS 1.73 BM t2g5 -2.0 o +2P
d6 4.90 BM t2g4 eg2 -0.4 o
d6 LS 0 BM t2g6 -2.4 o +2P
d7 3.87 BM t2g5 eg2 -0.8 o
d7 LS 1.73 BM t2g6 eg1 -1.8 o+ P
d8 2.83 BM t2g6 eg2 -0.1.2 o
d9 1.73 BM t2g6 eg3 -0.6 o
d10 t2g6 eg4 0
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 Significance of o and its physical measurement

Electronic spectrum of [Ti(H2O)6]3+

eg

3d14s0

t2g
494 nm = 20,300 cm-1
UV –Visible Spectroscopy
1 kj = 83.7 cm-1
[Ti(H2O)6]3+ o = 20,300 cm-1 = 243 kj/mol
Since an electron in the t2g set is stabilized
by -0.4 o 243 X -0.4 = -97 kj/mol
The complex is stabilized to the extent of
97 kj/mol compared to a hypothetical
spherical field due to the splitting of the d
orbitals; This extra stablization of the
complex is called crystal field stablization
t2g1eg0 t2g0eg1 energy (CFSE)
Because the sample absorbs most strongly around the green region of the visible spectrum, it appears purple. 21