Organic and Inorganic Chemistry

CYN-002
B. Tech I Yr. Courses

Dr. Dheeraj Kumar

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Coordination Chemistry

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 Coordination Compounds

Coordination compounds: composed of a metal

atom or ion and one or more ligands (atoms, ions,
or molecules) that are formally donating electrons
to the metal center.
• A ligand have at least one pair of electrons and is an electron
rich species, therefore, it is also called a Lewis Base or a
nucleophile.

• A Metal Cation is an electron deficient species and it can

accept a pair of electrons, therefore, a metal cation behaves
as a Lewis acid or an electrophile.

The coordination number of a complex depends on:

➢ The size of the central atom or ion.

➢ The steric interactions between the ligands.

➢ Electronic interactions between the central atom or ion and the ligands.
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 Addition Compounds

These are obtained by adding stoichiometric amounts of two or more

compounds. On the bases of there behavior in solutions they are divided into
(a) Double Salts or (b) Coordination Compounds.

Double Salts Coordination Compounds

• Loose their identity in solution. • Exist in crystalline as well as
• They will give tests of all their solution form (tends to retain their
constituents ions. identity)
• E.g. • They do not give the tests of all
their constituent ions in aq.
Solution
• E.g.

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 SELF STUDY
1. IUPAC Nomenclature of Coordination Compounds

2. Isomerism in Coordination Compounds

3.

4.

5.VALENCE BOND THEORY (VBT)

THESE TOPICS ARE NOT PART OF THE SYLLABUS (CYN002)
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Background requirement: +2 level CBSE/ICSE and JEE advanced
syllabus level

NCERT CHEMISTRY Class 12 Textbook Book 1 11

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 12
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 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

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, explains
Ajoydistortion
Ghatak 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
•Explains color, magnetism and energetics (does not predict shape)
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 Finding an explanation for the observed properties of transition metal complexes
using Crystal Field Theory

Variation of some physical properties of Magnetic properties of complexes

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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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 same17
 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
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[Fe(CN)6 ]4- d6 32200 19150 Low Spin o > P
 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/mol = 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
t2g1eg0 t2g0eg1 complex is called crystal field stablization
energy (CFSE)
Because the sample absorbs most strongly around the green region of the visible spectrum, it appears purple. 20
 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 = -2.4o +3P

CFSE = -2.0o +2P

CFSE = -2.4o +2P

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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Q1. For Mn3+ the electron pairing energy is 336 KJ/mol. The CFS for
[Mn(H2O)6]3+ is 250 KJ/mol. Will the complex have a high spin or low
spin complex. Explain in terms of CFSE.

Mn(25) = 3d5 4s2

Mn(+3) = 3d4

CFSE in High spin case: (t2g)3 (eg)1 = 3 X (-0.4 o) + 0.6 o = -0.6 o
= -0.6 X 250
= -150 KJ/mol

CFSE in Low spin case: (t2g)4 (eg)o = 4 X (-0.4 o) + 1P

= - 1.6 o + 1P
= - 1.6 X 250 + 336
= - 64 KJ/mol

Since, CFSE is higher in high spin case, therefore, high spin complex will be
formed.

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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)

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 Spectrochemical Series

I−< Br−< S2−< SCN−<Cl−< NO3−< N3−< F−< OH− <EtOH

< C2O42− ≈ H2O< NCS−< CH3CN <py<NH3<bipy<phen<NO2−

< PPh3< CN ≈ CO

Halide donors < O donors < N donors < C donors

• It is determined using spectroscopical studies keeping all other

factors constant.
Δ = 10 Dq = hν = hc/λ
• We can’t explain the position of all the ligands in this series. E.g. We
expect OH ˉ > H2O but it is opposite in the spectrochemical series.
• Using Molecular Orbital Theory (MOT), we can account for position of
each ad evert ligand.
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 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

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 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

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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

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Orientation of d-Orbitals in the Tetrahedral Environment

M L
L
L

4L approaches Metal d-orbitals

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d-orbitals Splitting in Tetrahedral Complexes
dxy, dyz, dzx
t2
+0.4Δt
Orbital Energy

Δt
Barycenter
Spherical Field −0.6Δt

e
dx2−y2, dz2
Free ion Metal ion in
Tetrahedral Field

Δt=(4/9) Δo 33
Features of Tetrahedral Geometry Compare to Oh Environment

(i) There are only 4 Ligands in the Td complex, and hence the ligand
field is roughly 2/3 relative to Oh

(ii) The direction of L approach in Td Complex doesn’t coincide

with the d-orbitals. This reduces the field by a factor 2/3.

Therefore, Δt is roughly 2/3 × 2/3 = 4/9 Δo

(iii) As a result, all tetrahedral complexes are high spin since the
CFS Smaller than the pairing Energy

(iv) Hence Low spin Configurations are rarely observed (e.g. Ni(CO)4.
Usually, if a very strong field ligand is present, the square planar
geometry favored (e.g., [Ni(CN)4]2-.

Examples: [FeCl4]−, [CoCl4]2−, [ZnCl4]2−, TiCl4, [MnO4]2−, [FeO4]2−

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CFSE and Electronic Arrangements in Tetrahedral Complexes
High Spin Situations Comparison to Oh
No. of d Environ.
electrons
e t2 CFSE (Δt) Δt=(4/9)Δo Weak Strong
Field Field
d1 −0.6 −0.27 −0.4 −0.4
d2 −1.2 −0.53 −0.8 −0.8
d3 −0.8 −0.36 −1.2 −1.2
d4 −0.4 −0.18 −0.6 −1.6
d5 0 0 0 −2.0

d6 −0.6 −0.27 −0.4 −2.4

d7 −1.2 −0.53 −0.8 −0.8
d8 −0.8 −0.36 −1.2 −1.2
d9 −0.4 −0.18 −0.6 −0.6
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d10 0 0 0 0