CYN-002

Coordination Chemistry
(7 lectures)
Crystal field theory, Crystal Field
Stabilization Energy, Explaining physical
properties, magnetic properties and
distortion of shape
Background requirement: +2 level CBSE/ICSE and JEE advanced syllabus level

NCERT CHEMISTRY Class 12 Textbook Book 1

NCERT CHEMISTRY Class 12 Textbook Book 1
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
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
•Explains color, magnetism and energetics (does not predict shape)
 Finding an explanation for the observed properties of transition metal complexes
using Crystal 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

 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 ii
orbitals to 2 sets due to an
octahedral field.
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 same
 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 – y 2 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
 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
o < P
[Fe(H2O)6 ]2+ d6 9350 19150 High Spin
[Fe(CN) ]4- d6 32200 19150 Low Spin o > P
 Significance of o and its physical measurement

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

3+
OH2 eg
H2O OH2
Ti 3d14s0
H2O OH2
OH2
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.
 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
 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

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
 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.
 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
Factors affecting the magnitude of crystal field
splitting, 

1. Nature of metal ion (row to which it belongs)

Going from the first row to second row there is an
increase in o : Larger the metal  larger is
the 

2. Oxidation state of the metal ion (higher the

oxidation state more is the o

3. Number of ligands and shape of complex

(Octahedral, tetrahedral, square planar….)

4. Relative strength of the ligand (Spectrochemical

Series)
 Factors Affecting the Magnitude of Crystal Field Splitting 

Size of the metal ion / Row to which the metal ion belong
Larger the size (row to which it belongs) larger the  value

[Co(en)3]3+ 23,200 cm-1

 50% increase
[Rh(en)3]3+ 34,600 cm-1
 25% increase

[Ir(en)3]3+ 41,000 cm-1

Consequence:
Second and third row transition metals will have greater tendency to
form low spin complexes

Reason:
Around a large metal ion, a given set of ligands experience less steric
crowding and therefore can approach closer to the metal ion. More
closer- larger will be the splitting
 Factors Affecting the Magnitude of Crystal Field Splitting 

Charge on the metal ion / Oxidation state of the metal ion

Greater the charge larger the  value

[Co(NH3)6]2+ 10,000 cm-1 [Cr(H2O)6]2+ 14,000 cm-1

[Co(NH3)6]3+ 22,900 cm-1 [Cr(H2 O)6]3+ 17,400 cm-1

Reason:
Higher the charge on the metal, the ligands are pulled in towards
the metal more and therefore the ligands split the energies of the
metal d orbitals to a greater extent
Factors Affecting the Magnitude of Crystal Field Splitting 

Number of ligands around the metal and shape of complex

(Octahedral, tetrahedral, square planar….

SP  1.74 O
 Splitting of d-orbitals by a tetrahedral field and a square planar
field of ligands.

t2

e
tetrahedral square planar

Square planar is related to

Tetrahedron is related to cube octahedral splitting:
in splitting of energy levels Removing the axial ligands of
t =1/2 C an octahedron to infinity
Same arrangement of orbitals results in a square plane
Factors affecting ; Strength of the Ligand

The effect of different ligands on

the degree of  splitting is
understood from the UV-Vis
absorption spectra of complexes
of the same metal-ion with
different ligands

There is an increase in the

frequency of the 1 (o)
absorption band as the ligands
on Cr3+ is changed from
F  O based N based ligands
 The Spectrochemical series
I  < Br  < S2- < SCN  < Cl  < F  < OH  < Ox < ONO  < H2O Weak field
< NCS < edta 4
< NH3  Py < en < bipy < Phen < NO2  < PPh3 < CN-  CO Strong
field
Halides ; sulfur donors < Oxygen donors < Nitrogen donors < CN-, CO

COBALT(III) Complexes of
(a) CN–, (b) NO2–, (c) phen, (d) en, (e) NH3, (f) gly, (g) H2O, (h) ox2–, (i) CO32– Stepwise addition of ‘en’ to [Ni(H2O)6]2+
 Crystal Field theory to explain observed properties of complexes:
Variation of some physical properties across a period:

1. Lattice energy of transition metal ions in a complex

2. Ionic radii of transition metal ions in a complex
3. Enthalpy of hydration of transition metal ions
4. Site preference of Spinels and Inverse spinels

Lattice Energy: Energy released when one mole of an ionic solid is formed from isolated gaseous ions

Calculated theoretically using the Experimentally determined using

Born- Lande Equation the Born- Haber cycle

Where
A = Madelung constant ( related to the geometry of the crystal)
N = Avogadro’s number
Z= Charge on the M+ and M- ions
e 0= permittivity of free space
r0 = distance to the closest ion
n= Born exponent (a number between 5 and 12)
Lattice Energies (1st Row Divalent Transition Metal Halides and Main group
halides)

Compound Lattice energy (KJ/mol) Differences

Measured Calculated (KJ/mol)

NaCl -764 -764 0

MgF2 -2908 -2915 +7

MnF2 -2770 -2746 +24

FeF2 -2912 -2752 -160

CuF2 -3042 -2885 -157

-3046 transition
NiF2for a six- coordinate
The discrepancy -2917
metal ion can-129
be explained by CFSE
•According to the Born –Lande Equation one can expect a smooth increase in lattice
energies as we go from left to right due to decrease in ionic radius of the metal ions
•As anticipated a smooth curve is not seen: instead a double hump shaped curve is
obtained
•Ca2+ (d0), Mn2+(d5 HS) and Zn2+ (d10) which in common have CFSE =0 lie almost on the
expected line.
•Ions such as V2+ which show high CFSE in a weak field situation with high lattice
energy values show significant deviation from the calculated lattice energies
Ionic radii of transition metal ions in the presence of weak field and strong field ligands

One can expect decrease the ionic radii of the M 2+ ions smoothly from Ca2+
to Zn 2+ due to the increase in nuclear charge

But the plot shown below (left) for weak field ligands indicate that the
expected regular decrease is absent expect for Ca2+, Mn 2+ and Zn 2+

For strong field ligands like CN- a different trend in variation is observed
with a steady decrease till d6 (t2g6)

+2 Oxidation +3 Oxidation
state state
Ionic radii of transition metal ions in the presence of weak field and strong field ligands

Why does the ionic radii decreases and then

increases??

Ti2+ (d2) electron occupy only t2g

V2+ (d3) electrons occupy only t2g
Cr2+ (d4HS) electrons start occupying the eg
orbitals

As the eg orbitals point directly towards the

ligands, the repulsion between the metal
electrons and ligand electrons will be higher
than normal leading to the eventual increase
in the ionic radius.

In the case of strong field ligand such as

cyanide there will be a steady decrease in
ionic radii till t2g6 is reached.

The same tend is observed also for M3+

transition metal complexes
 Variation of some physical properties across a period
Enthalpy of hydration of transition metal ions

It is the heat exchange involved when 1 mole of gaseous ions become hydrated
M(g)2+ + excess H2O [M(H2O)6]2+
The amount of energy released when a mole of the ion dissolves in a large amount
of water forming an infinite dilute solution in the process.
Higher the charge on the ions and smaller the size, more exothermic will be the
hydration energy. So it is expected to increase smoothly on going from left to
right of the transition metals (green line in the graph)

The heats of hydration

show two “humps” consistent
with the expected CFSE for the
metal ions. The values for d5 and
d10 are the same as expected with
a CFSE equal to 0.
Site preference of Spinels and Inverse Spinels

Spinels are a class of crystalline solids of the

general formula AB2O4 (AIIB III2O4 ) where
A = main group B= main group
(Group IIA) or (Group IIIA) or
transition metal ion transition metal ion
in the +2 oxidation in the +3 oxidation
state state
The weak field oxide ions provide a cubic close-
packed (CCP) lattice. In one unit cell of AB2O4 there
are 8 tetrahedral and 4 octahedral holes

Normal Spinel: A2+ Inverse Spinel: The +2

ions occupy 1/8th of the Td ion and one of the +3 ions
holes exchange positions
B3+ ions occupy ½ of the i.e. Td holes: +3 ,
octahedral holes Oh holes: both +2 and +3 ions

Eg. MgAl2O4 Eg. Fe3O4 (Magnetite)

Fe3+ Tetrahedral
Mg2+ Tetrahedral
Fe 2+, Fe3+ octahedral
Al3+ octahedral
If A and B of AB2O4 are both s or p block elements (e.g. MgAl2O4) it always show
Spinel structure

Question: Why does some AB2O4 compounds having transition elements

as A and /or B prefer the inverse Spinel structure and some others normal
Spinel structure?

ANS: Crystal Field Stabilization Energy in an octahedral site [Also given as Octahedral site
stabilization energy (OSSE) in some books]

Mn3O4 = MnIIMnIII2O4 Fe3O4 = FeIIFeIII2O4

O2- = a weak field ligand Fe2+ = d6 HS : CFSE =-0.4 o

Mn2+ = d5 HS : CFSE = 0 Fe3+ = d5 HS: CFSE = 0
Mn3+ = d4 HS : CFSE = -0.6 o
Fe2+ by exchanging positions
Mn2+ by exchanging positions with Fe3+ to an octahedral hole
with Mn3+ in an octahedral hole is going to gain extra crystal
is not going to gain any extra field stabilization energy. While
crystal field stabilization energy. Fe3+ by being in the octahedral
While Mn3+ by being in the hole will not have any CFSE.
octahedral hole will have CFSE. Therefore Fe3O4 will be Inverse
Therefore Mn3O4 will be Normal Spinel
 Magnetic properties of transition metal complexes

Magnet on:
Paramagnetic
Magnet off

Magnet on: Gouy balance to measure

diamagnetic the magnetic
susceptibilities

32
 Magnetic properties of metal complexes
Magnetism is caused by moving charged electrical
particles (Faraday, 1830s). These particles can be the
current of electrons through an electric wire, or the
movement of charged particles (protons and electrons)
within an atom. These charged particles move much like
planets in a solar system:
nucleus spin around its own axis, causing a very weak
magnetic field.
electrons orbit around the nucleus, causing a weak
magnetic field.
electrons spin around their own axis, causing a
significant magnetic field .
Spinning electrons generate the bulk of the magnetism in
an atom.
Within each orbit, electrons with opposite spins pair
together, resulting in no net magnetic field.
Therefore only unpaired electrons lead to magnetic
moment

The spin-only formula (μs) s  n(n  2)

 Magnetic properties: Spin only and effective

The spin-only formula (μs) applies reasonably well to metal ions from the
first row of transition metals: (units = μB,, Bohr-magnetons)

Metal ion dn configuration μs(calculated) μeff

(observed)
Ca2+, Sc3+ d0 0 0
Ti3+ d1 1.73 1.7-1.8
V3+ d2 2.83 2.8-3.1
V2+, Cr3+ d3 3.87 3.7-3.9
Cr2+, Mn3+ d4 4.90 4.8-4.9
Mn2+, Fe3+ d5 5.92 5.7-6.0
Fe2+, Co3+ d6 4.90 5.0-5.6
Co2+ d7 3.87 4.3-5.2
Ni2+ d8 2.83 2.9-3.9
Cu2+ d9 1.73 1.9-2.1
2+ 3+ 10
 Spin and orbital contributions to μeff
For the first-row d-block metal ions the main contribution to magnetic susceptibility is
from electron spin. However, there is also an orbital contribution (especially for the
second and third row TM) from the motion of unpaired electrons from one d-orbital to
another. This motion constitutes an electric current, and so creates a magnetic field.
spinning d-orbitals
electrons

spin contribution – electrons are orbital contribution - electrons

spinning creating an electric move from one orbital to
current and hence a magnetic field another creating a current and
hence a magnetic field
 Crystal Field theory explains magnetic moments of TM complexes

Strength of the ligand, type of complex , size of the metal and its oxidation state
affects crystal field splitting
 Temperature dependence of magnetic moments

Fe(Phen)2(NCS)2

How crystal field theory explains temperature dependence of eff

Fe2+ = d6
 IITD 2015 L2-S42

Problem solving !!

Cobalt form three octahedral complexes, [MCl6]4-,

[M(R2NCS2)3] and [M(CN)5(H2O)]3-. These have
magnetic moments 0, 1.73 and 3.9 BM (not in the
order). Assign the moments to the complexes and
predict the relative strength of the
dithiocarbamate ligand.

Solution
[CoCl6]4- Co2+, 3d 7 ,Cl- weak ligand, HS, 3 unpaired e’s ~ 3.9 BM
[Co(CN)5(H2O)]3-. Co2+, CN- strong ligand, LS 1 unpaired e 1.73 BM
[Co(R2NCS2)3], Co3+, 3d 6 , 0 BM means ligand is strong field and low spin
complex
 IITD 2015 L2-S43

Distortion of some octahedral complexes

All six Ni-O bonds two long axial

equal at 2.05 Å Cu-O bonds
= 2.45 Å

four short
in-plane
Cu-O bonds
[Ni(H2O)6]2+
= 2.00 Å
[Cu(H2O)6]2+
no distortion
distortion lengthens axial Cu-O’s
 Orbital Degeneracy versus Electronic Degeneracy

Orbital degeneracy: The 5 d orbitals are of the

same energy in spherical field. This orbital

Energy
degeneracy is lifted (reduced) in an octahedral 5 d orbitals in a
field (to t2g and eg ) spherical field

Electronic Degeneracy : Case of t2g1 Electronic Degeneracy : Case of t2g3

Here there are three different ways by which the Here there is only one way by
single electron can occupy the t2g orbitals. There are which the three electron can
three possible electronic configurations which are of occupy the t2g orbitals. So there is
the same energy. Electronic degeneracy is present no electronic degeneracy

eg eg eg eg

t2g t2g
t2g t2g
 Orbital Degeneracy versus Electronic Degeneracy

Orbital degeneracy: The 5 d orbitals are of the

same energy in spherical field. This orbital

Energy
degeneracy is lifted (reduced) in an octahedral 5 d orbitals in a
field (to t2g and eg ) spherical field

Electronic Degeneracy : Case of t2g1 Electronic Degeneracy : Case of t2g3

Here there are three different ways by which the Here there is only one way by
single electron can occupy the t2g orbitals. There are which the three electron can
three possible electronic configurations which are of occupy the t2g orbitals. So there is
the same energy. Electronic degeneracy is present no electronic degeneracy

eg eg eg eg

t2g t2g
t2g t2g
 Ni(II) Cu(II)

High-spin Ni(II) – only one way

Cu(II) – two ways of filling the eg level
of filling the eg level
– it is electronically degenerate
– not electronically degenerate
Cu(II) d9
Ni(II) d 8

eg eg
eg
Energy

t2g t2g t2g

What is the consequence of ELECTRONIC DEGENERACY ?

 Distortion of the shape of complexes:
The Jahn-Teller Effect
Hermann Arthur Jahn
English Scientist of German Edward Teller
Origin father of the hydrogen bomb

The Jahn–Teller theorem states that any nonlinear molecule with an Director of Lawrence Livermore
National Laboratory

electronic degenerate ground state will undergo a geometrical

distortion that removes the degeneracy, lowers the symmetry because
the distortion lowers the overall energy of the species.

The Jahn-Teller effect predicts which

structures will distort. It does not
predict the nature or extent of the
distortion. The effect is more significant
when the electronic degeneracy is in the
orbitals that point directly towards the
ligands.

" H. Jahn and E. Teller (1937). "Stability of Polyatomic Molecules in Degenerate Electronic States. I. Orbital
Degeneracy". Proceedings of the Royal Society A 161 (905): 220–235.
 Degeneracy in the t2g orbital
Not so significant Jahn Teller distortion
Distortion manifested as the
eg Splitting of UV Vis peaks

Rb2Na[TiCl6]
Ca2K [TiCl6]
[Ti(H2O)6]3+ Rb3[TiCl6]
t2g
No Measurable differences in
bond lengths

Degeneracy in the eg orbital

Cu
Significant Jahn Teller distortion F
eg
193 pm

227 pm

t2g
Measurable differences
in bond lengths
 d-Electron configurations which show Jahn Teller distortions

d1 d2 d3 d4 d5

HS NO electronic
degeneracy:
NO Jahn Teller
Distortion

LS

Normal Jahn
Teller Distortion
d6 d7 d8 d9 d10 Degeneracy in t2g

HS
Significant Jahn
Teller Distortion
Degeneracy in eg

LS
 Structural effects of Jahn-Teller distortion on [Cu(en)3]2+

N
N
N Short
in-plane
Cu-N
Cu
bonds of
N 2.07 Å

N
N
long axial Cu-N
bonds of 2.70 Å

Chelation versus Jahn Teller distortion : Two opposing forces

consequence: low stability of such complexes
Tetragonal z out distortion extended : The Square Planar Case
 Problem solving!
[Co(en)3]2+, [Fe(CN)6]4, [Fe(CN)6]3-, [CrF6]4
Classify the above given octahedral complexes and write in the boxes below as tho se

Having no tetragonal Having slight Having significant tetragonal

distortion tetragonal distortion distortion indicated as varying
which is seen from UV bond distances in their
Visible spectral studies structure

[Co(en)3]2+ Co = 3d
2+ 7
eg
Electronic degeneracy in the eg
en=strong field
orbital =
Significant Jahn Teller distortion
t2g