CHEM F111 GENERAL CHEMISTRY

Instructor-in-charge : MAINAK BANERJEE

Instructors: Bhavana. P., Ranjan Dey, R. N. Behera, Jayadevan. K. P.,
Subhadeep Banerjee, Tincy Lis Thomas, Venkatesan. S. Thimmakondu,
Tanmoy Mandal
Text Books:
J. D. Lee, Concise Inorganic Chemistry, 5th Edition, Blackwell Science,
Oxford, 1999.
T. W. Graham Solomons and Craig B. Fryhle, Organic Chemistry,
10th Edition, John Wiley & Sons, Inc. New York, 2011.
P.W. Atkins, Elements of Physical Chemistry: 6th Edition,
Oxford University Press, 2015.

Chemistry of
coordination
complexes

Key Contents
Werners work and recent studies of complex
Effective Atomic Number (EAN)

Valence Bond Theory

Crystal Field Theory
Jahn-Teller distortion
Chelates
Isomerism
3

Inorganic compounds

Simple salts e.g. NaCl

Addition compound - two types
Double salts: Lose identity in solution;

e.g. potassium alum K2SO4. Al2(SO4)3. 24H2O

Coordination complexes: Retain identity in solution;

e.g.

Fe(CN)2 + 4KCN

K4[FeCN]6

Coordination Complex
structure consisting of a central atom or ion ,
bonded to a surrounding array of ligands
The atom within a ligand that is directly bonded
to the central atom or ion is called the donor atom.
A ligand donates at least one pair of electrons to the
central atom/ion.
Compounds that contain a coordination complex are
called coordination compounds

d-Block Transition Elements

IIIB IVB

VIIIB

VB VIB VIIB

Cr Mn Fe

IIB

Sc

Ti

Zr

Nb Mo

Tc

Ru Rh Pd Ag Cd

La

Hf

Ta

Re

Os

Co

IB

Ir

Ni Cu Zn

Pt Au Hg

Most of them have partially occupied d

orbitals in common oxidation states
6

Transition Metals

Characteristics due to d electrons:

Exhibit multiple oxidation states (0 to +7)

Compounds typically have color
Exhibit interesting magnetic properties

Coordination Chemistry

Ligands

classified according to the number of donor atoms

Examples

monodentate = 1
bidentate = 2
tetradentate = 4
hexadentate = 6

chelating agents

Ligands

Monodentate

Examples:

Example Complexes

10

H2O, CN-, NH3, NO2-, SCN-, OH-, X- (halides), CO, O2[Co(NH3)6]3+

[Fe(SCN)6]3-

M
E
T
A
L

S
T
R
U
C O
T F C
U
O
R
M
E
P
L
E
X

Werners work
Coordination complexes were long known although not
understood e.g. Prussian blue and copper vitriol.
The key breakthrough occurred when Alfred Werner

proposed his theory in 1893 to predict structure of these

complexes.
His brilliance showed the way to predict right structure
even before the electron is known (was discovered by
Thompson in 1896)
He proposed two different valencies for coordination
complexes

Primary valencies : nondirectional

Secondary valencies : directional
(coordination number of the complex)

11

Metal Complexes used by Werner

Four different cobalt ammonium complexes were
known, which were used by Werner to establish his theory
Complex

Color

CoCl3.6NH3

Yellow

CoCl3.5NH3

Purple

CoCl3.4NH3

Green

CoCl3.4NH3

Violet

early name

Luteo complex

Purpureo complex
Praseo complex

Violeo complex
12

Experiments done by Werner

Treatment with excess AgNO3 solution: resulted in different
amount of precipitated AgCl
CoCl3.6NH3 + excess AgNO3

3 AgCl

CoCl3.5NH3 + excess AgNO3

2 AgCl

CoCl3.4NH3 + excess AgNO3

1 AgCl
(for either praseo or violeo complex)

Werner's Conclusion
central metal atom in complex has two types of valencies,
Primary valency and Secondary valency.
13

Possible structures for C. N. = 6

Hexagonal

Triagonal prism

Octahedral

14

No. of isomers expected and found for C. N. = 6

Formula

Planar

triagonal prism

Octahedral

Experimental
1

[MX6]

-----------------------------------------------------------------------------------------------------------------[MX5Y]

-----------------------------------------------------------------------------------------------------------------2

[MX4Y2]

cis

trans

-----------------------------------------------------------------------------------------------------------------2
[MX3Y3]

fac

mer

15

Possible
structures for C. N. = 4
t

Tetrahedral

square planar

16

No. of isomers expected and found for C. N. = 4

Formula

Tetrahedral

square planar

MX2Y2

trans

experimental

cis

trans structure has no dipole moment

cis structure has dipole moment

e.g. [Pt(NH3)2Cl2] and [Pd(NH3)2Cl2]

H3 N

H3 N

m=0

Cl
Cl

Cl
H3 N

m=0

NH3

Cl
17

Summary of Werner's Work:

The central metal atom in complex has two types of valencies,

Primary valency and Secondary valency.
Primary valencies are ionizable whereas secondary valencies non-ionizable
In complexes, the ligands are projected in space about the central metal
atom to give a specific shape to the complex.

18

Recent methods of studying complexes

1. Simultaneous measurement of molar conductivity
and freezing point depression
Molar conductivity measurement
Depends on (a) concentration of solute

(b) number of charges on the species formed on dissolution

Molar Conductivities of salt and complexes (at 0.001M concentration)

ohm-1 cm2 mol-1

LiCl
CaCl2
CoCl3.5NH3
CoBr3.5NH3
LaCl3
CoCl3.6NH3
CoBr3.6NH3

Li+ ClCa2+ 2Cl-

La3+ 3 Cl-

Total of 2 charges
Total of 4 charges

112.0
260.8
261.3
257.6

Total of 6 charges

393.5
431.6
426.9
19

Cryoscopic measurement

It involves measurement of how much freezing point is lowered

Depends on the number of particles present in solution

Establishment of structure of complexes

20

Other methods
Measurement of magnetic moment
Measurement of dipole moment
e.g. for [Pt(NH3)2Cl2]
cis form have dipole moment
trans form does not have any dipole moment

The most powerful and modern technique for the

determination of crystal structure is Single Crystal
X-ray diffraction
21

Effective Atomic Number

exceptions

Sidgwick suggested that electron pairs from ligands were added until the central
metal was surrounded by the same number of electrons as the next noble gas

22

d orbitals

23

Valence Bond Theory

A covalent bond forms when the orbtials of two

atoms overlap and are occupied by a pair of
electrons that have the highest probability of
being located between the nuclei.

Linus Carl Pauling

(1901-1994)
Nobel prizes: 1954, 1962

24

Valence bond theory for coordination complex

metal form coordination bond with the ligand i.e. bonding is due to
donation of a pair of electron of ligand to metal

Resulting a s bond
between metal and
ammonia

VB theory can explain SHAPE, MAGNETIC PROPERTY etc.

of the metal complexes
25

Valence Bond Theory

Metal or metal ion: Lewis acid
Ligand: Lewis base
Hybridization of orbitals

C.N. Geometry
4
4
5
6

tetrahedral
square planar
trigonal bipyramidal
octahedral

Hybrids
sp3
dsp2
dsp3 or sp3d
d2sp3 or sp3d2
26

Valence Bond Theory

s, p and d orbitals mix to give hybrid orbitals with specific geometries

Octahedral Complex
[Cr(NH3)6]3+

27

Explanation of structures by VB theory

[CoF6]3
Co [Ar] 3d7 4s2
Co3+ [Ar] 3d6

3d

Outer orbital complex

4s

4p

4d

sp3d2 hybridisation
octahedral
The complex is paramagnetic
28

Explanation of structures by VB theory

[Co(NH3)6]3+
Co [Ar] 3d7 4s2
Co3+ [Ar] 3d6

3d

Inner orbital complex

4s

4p

4d

d2sp3

octahedral
The complex is diamagnetic
29

Explanation of structures by VB theory

[PtCl4]2, diamagnetic
Pt2+ [Xe] 4f14 5d8
5d

6s

6p

dsp2
square planar

30

Explanation of structures by VB theory

[NiCl4]2, tetrahedral
Ni2+ [Ar] 3d8
3d

4s

4p
sp3

paramagnetic

31

Limitations of VB theory

The color of the metal complex can not be explained

Can not explain why the magnetic property vary with temperature

32

Crystal Field Theory

Proposed by Bethe and van Vleck
Interaction between metal and ligand is purely electrostatic
i.e. bonding is due to ion-ion attraction if ligand is ionic or ion-dipole
attraction if ligand is neutral
Explain the electronic spectra and magnetism of the transition metal
complexes

Assumptions
The ligands are considered as point charges
There is no overlap between metal and ligand orbitals
All the d orbitals on the metal have same energy in the free atom.
The ligands destroy the degeneracy of the orbitals
33

The approach of ligands in an octahedral

complex

34

The approach of ligands in an octahedral

Complex contd

35

Splitting of d-orbitals in an
octahedral field
eg
Energy

d-orbitals split
Into two groups

t2g

Free metal

Metal ion in octahedral field

36

Energy level of d orbitals in an octahedral field

+0.6 D0

D0 or 10Dq

Bary centre (average energy level)

Average energy of
metal ion in spherical
field

+0.4 D0

Metal ion in octahedral field

eg orbitals (dx2-y2 and dz2) get more repulsion by six

approaching ligands and increase their energy level than the spherical
field.
t2g orbitals (dxy, dxz and dyz) get stabilized than the d-orbitals in the
spherical field as they are situated in between the axes.
37

Crystal Field Theory

Distribution of electrons
d2

d3

d4

38

How the complexes are colored?

Why [Ti(H2O)6]3+
appear purple

The 3d electron of [Ti(H2O)6]3+ is excited from the

lower-energy d orbitals to the higher-energy ones
when irradiated with light of 510-nm wavelength

d-d transition gives a single broad peak

with maxima at 20300 cm-1
The value of D0 is 243 kJ/mol
(1 kJ/mol = 83.7 cm-1)

UV and Visible absorption spectrum of [Ti(H2O)6]3+

This is a convenient way of

measuring D0
39

Crystal Field Stabilization Energy (CFSE)

A convenient way of measuring D0 is converting the absorption
maximum of the complex into energy. CFSE is obtained from D0.
For [Ti(H2O)6]3+ the single electron is situated at the t2g level
CFSE = -0.4 x D0
= -0.4 x 243 = -97 kJ/mol

For [Cr(CN)6]3- what is CFSE if it absorbs at 26280 cm-1?

All three electrons are situated at the t2g level
CFSE = -3 x 0.4 x D0
= -3 x 0.4 x 26280/ 83.7 = -376.77 kJ/mol
CFSEOh = (-n(t2g) x0.4 + n(eg) x0.6) x D0

1 kJ = 83.7 cm-1
40

Colors of Transition Metal Complexes

white
light

red light
absorbed

green light
observed

41

Complementary colours

absorbed
color

observed
color

[Ti(H2O)6]3+ absorbs yellow-green colour (490 nm = 20400 cm-1) and thus

appears purple (red-violet)

Color of Transition Metal Complexes

Different complexes exhibit different

colors
color of light absorbed depends on D

larger D = higher energy light absorbed

Shorter wavelengths

smaller D = lower energy light absorbed

Longer wavelengths

43

Crystal Field Stabilization Energy (CFSE)

The magnitude of D0 depends on four major factors

Nature of the ligands

Charge on the central metal ion
Whether the metal is in the 1st, 2nd or 3rd row of transition elements

Nature of the ligands

Crystal field splitting of various ligands with same metal ion

44

spectrochemical series
It is possible to arrange ligands in a series that reflects their
ability to split the d-orbitals.

Weak field ligands

I- < Br- < S2- < Cl- < NO3- < F- < OH- < EtOH < oxalate < H2O < EDTA
< (NH3 and pyridine) < en < dipyridyl < o-phenanthroline < NO2- <
CN- < CO
Strong field ligands

pattern of increasing s donation

Halide donors < O donors < N donors < C donors

45

 Charge on the central metal ion

Whether the metal is in the 1st, 2nd or 3rd row of transition elements

46

Crystal Field Stabilization: Weak

Field and Strong Field
For d 4 two configuration are possible i) t2g3 eg1 or ii) t2g4 eg0
In weak field
CFSE = - 3x0.4xD0 + 1x0.6xD0 = -0.6 D0

In strong field
CFSE = - 4x0.4xD0 = -1.6D0
Total SE = -1.6D0 + P
P = pairing energy

a) d 4 high-spin arrangement; b) d 4 low-spin arrangement

47

Pairing energy
Depends on two factors

The electronic repulsion in metal d-orbitals forcing two electrons to

occupy same orbital
The exchange energy to reverse the spin
For a given metal ion P is constant

48

CFSE and electronic arrangement of octahedral complexes

49

Magnetism

It is assumed that it arises

entirely from unpaired electron
spin

if there is n no. of electrons

spin only magnetic moment,

Spin only moment is valid for

1st row transition elements.
Temperature dependence is
explained by spin-orbit coupling

50

Effects of Crystal Field Splitting

Lattice energies of metal
complexes vary due to
crystal field stabilization

-U (KJ/mol)

F
CFSE
Cl
Br
I

Lattice energies of the metal halides (MX 2)

of the first transition series. Vertical bars
indicates uncertainties in experimental values

51

Effects of Crystal Field Splitting

contd.

Enthalpy of hydration
-2200
-2000
-1800
-1600

Enthalpies of hydration for M2+

52

Effects of Crystal Field Splitting

contd.

Octahedral ionic radii of M2+ vary with crystal field

splitting

53

Effects of Crystal Field Splitting contd

.

54

Tetrahedral complexes

55

Tetrahedral complexes

There are four ligands instead of six

The direction of the orbitals does not
coincide with the direction of the ligands

Dt = (4/9) Do (each point contribute 2/3 factor to tetrahedral field)

When tetrahedral complexes are

favored?

57

CFSE and electronic arrangement of

tetrahedral complexes
e

t2

mD

Dt

58