Transition Metal Chemistry and

Coordination Compounds

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The Transition Metals

22.1
 Oxidation States of the 1st Row Transition Metals
(most stable oxidation numbers are shown in red)

Transition metals
generally shows variable
oxidation states
(Except 1st and last
element of the series)

22.1
Scandium Titanium Vanadium

Chromium Manganese Iron

Cobalt Nickel Copper 22.2

General characteristic of Transition metals:

1. Electronic configuration: The valence shell electronic

configuration of transition metal is ns1-2(n-1)d1-10.
2. Oxidation state: Transition metal shows variable oxidation
state due to the participation of outer valence shell [i.e. ns
and (n-1)d ] electrons for compound formation.
3. Formation of complexes: Most of the transition metal ion have
capacity to form complex because of small size and vacant d-
orbital. Ex: [Fe(CN)6]4- = hexacyanoferrate(II) ion
4. Colour formation: The transition metal forms colour compound
which is due to the d-d transition of electron which lies in
visible region of spectrum.
5. Magnetic property: Most of the transition metal compound are
paramagnetic due to the presence of one or more unpaired
electrons in d-orbital. But, if unpair electron in not
available in d-orbital, it is diamagnetic in nature.
6. They are good at their catalytic activity.
7. Transition metals are hard, malleable, ductile, lusterous and good
conductor of heat and electricity. They have capacity to form an alloy.
They have high m.p. , b.p. and high density.
Complex or Co-ordination compound

Co3+

2+4=6
 Coordination Compounds
A coordination compound typically consists of a complex ion
and a counter ion.
A complex ion contains a central metal cation bonded to one
or more molecules or ions.
The molecules or ions that surround the
metal in a complex ion are called ligands.

A ligand has at least one unshared pair

of valence electrons

••
O N •• -
••

••
••

C O
••

Cl
H H H H H ••

22.3
 SHAPE OF COMPLEX IONS
Alfred Werner (in 1893), put
forwarded a theory for explanation of
co-ordination compounds. The basic
postulates of Werner’s theory were;

1. Metal in complex ion possesses two

types of valencies primary valence
(ionisable) and secondary valence
(non-ionisable). The primary
valence corresponds to oxidation
number and secondary valence
corresponds to co-ordination
number.

2. The secondary valencies are always

directed to fixed position in space
about the central metal ion. The
number and arrangement of ligands
gives structure of complex ion.
 Structure of Coordination Compounds

Coordination number Structure

2 Linear
4 Tetrahedral or Square planar

6 Octahedral
22.4
According to Sidwick, metal ion will continue accepting
electron pairs till the total no. of electrons in metal ion is
equal to the next higher noble gas. The total no. of electron is
called effective atomic number (EAN) of metal.

EAN = (Atomic no. – Oxidation state) + (no. of ligand x 2)

For example, [Co(NH3)6]3+

atomic no. of Co = 27
Oxidation state of Co = +3
total no. of electrons in Co3+ = 27-3 = 24
one NH3 contributes 2 electrons to Co ion.
total electrons contributed by NH3 = 6 x 2 = 12.

Hence, EAN = 24 + 12 = 36.

 Coordination Compounds
The atom in a ligand that is bound directly to the metal atom is
the donor atom. ••
O N
H H H H H

The number of donor atoms surrounding the central metal atom

in a complex ion is the coordination number.
Ligands with:
one donor atom monodentate H2O, NH3, Cl-
two donor atoms bidentate ethylenediamine
three or more donor atoms polydentate EDTA

22.3
 Coordination Compounds

bidentate ligand polydentate ligand

(EDTA)
•• ••
H2N CH2 CH2 NH2

Bidentate and polydentate ligands are called chelating agents

22.3
22.3
 What are the oxidation numbers of the metals in
K[Au(OH)4] and [Cr(NH3)6](NO3)3 ?

OH- has charge of -1

K+ has charge of +1
? Au + 1 + 4x(-1) = 0 NO3- has charge of -1
Au = +3
NH3 has no charge

? Cr + 6x(0) + 3x(-1) = 0

Cr = +3

22.3
Rules for Naming Coordination Compounds

[Co(NH3)5Cl]Cl2
1. Cation is named before the anion.
2. Ligands are named before the metal ion.

3. For negatively charged ligands, an “o” is added to the root

name of an anion (such as fluoro, bromo, chloro, cyano,
hydroxo, etc.).

4. When several ligands of a particular kind are present, the Greek prefixes di-,
tri-, tetra-, penta-, and hexa- are used to indicate the number of ligand. If
the ligand already contains a Greek prefix, then prefixes bis, tris, and
tetrakis are used to indicate the number of ligand.
penta ammine
22.1
22.3
 What is the systematic name of
[Cr(H2O)4Cl2]Cl ?

tetraaquodichlorochromium(III) chloride

Write the formula of

tris(ethylenediamine)cobalt(II) sulfate

[Co(en)3]SO4

22.3
 5. The oxidation state of the central metal ion is designated by a Roman
numeral:
cobalt (III)
6. When more than one type of ligand is present, they are named
alphabetically:
pentaamminechloro
7. If the complex ion has a negative charge, the suffix “ate” is added to the
name of the metal.

The correct name is:

pentaamminechlorocobalt(III) chloride
Syntax:
1. Anionic complex: [ cation + ligand(alphabetical order) + metal + ate ( valency)
K3[Fe(CN)6] Na4[ Ni(CN)4] K2[ HgI4 ]

2. Cationic complex: [ ligand(alphabetical order) + metal ( valency) + anion.

[Co(NH3)6]Cl3 [CrCl2(H2O)4]Cl [Cu(en)2]SO4
3
 4. Coordination Isomerism

➢ The isomerism due to the interchange of ligands between the

positive and negative part of the coordination sphere is called
coordination isomerism.
➢ Coordination isomerism is shown by the complexes in which both
positive and negative parts are complex species.

Example 1: [Co(NH3)6][Cr(C2O4)3] and [Co(C2O4)3][Cr(NH3)6]

Example 2: [Co(NH3)6][Cr(CN)6] and [Co(CN)6][Cr(NH3)6]
Identify type of isomerism
1.[CoCl(H2O)(NH3)4]Cl2 and
[CoCl2(NH3)4]Cl.H2O
2. [Cr(SCN)(H2O)5]2+ and
[Cr(NCS)(H2O)5]2+
Inner orbital
complex

Ex;
[Cr(NH3)6]3+
[Fe(CN)6]4-

Outer orbital
complex

Ex;
[Cu(NH3)6]2+
[Fe(H2O)6]3+
Following assumptions are made in CFT;
1. Ligands are treated as point charges.
2. There is no interaction between metal orbital and ligand orbitals.
3. The arrangement of ligands around the central metal ion is such that the
repulsion between these negative point is minimum.
4. The five d-orbital in an isolated gaseous atom/ions are degenerate i.e.
they have equal energies. If a spherically symmetrical field of negative
charge is place around the metal, the orbital remain degenerate.
5. In asymmetric field of ligand (say octahedral field), d-orbital splits into
two sets i.e. t2g and eg with energy difference of Δo .
6. For strong field ligand Δo is large and for weak field ligand Δo is small.

What is d-orbital degeneracy? How the nature of ligands remove

degeneracy of d-orbitals into two sets t2g and eg?
Crystal field splitting in Octrahedral complexes:
In case of octahedral complexes, metal is at the center of octahedron and ligands are at the six
corner of octahedron.
There occurs repulsion between electrons in metal d-orbital and electrons of ligands. Such
repulsion is more when metal d-orbitals are directed towards the ligands than when it is away form
ligands.
The splitting of central metal d-orbital into two sets (i. e, t2g and eg ) due to repulsion effect of ligand
when approaching towards central metal cation is known as crystal field splitting.

Thus, dx2-y2 and dz2

orbitals that are directed
towards x, y and z axes
experiences more
repulsion and energy is
raised.

The dxy, dyx and dxz orbital

lie in between axes will be
lowered in energy relative
to average energy in
crystal field. Thus,
degeneracy of d-orbitals
removed in two sets.
➢ The energy between t2g and eg is called Δo ( o for octahedral).
➢ The value of Δo depends on field given by ligand and charge of metal
ion.
➢ In metal ion complex; for strong field ligand, Δo is large and for weak
field ligand, Δo is small.

Ligands in increasing field strength in

spectrochemical series is;

I- < Br- < S- - < NO3- < F- < OH- < oxalate (C2O4)- - <
H2O < EDTA < NH3 < ethylenediamine (en) < NO2 <
CN- < CO .
What is spectrochemical series?
The series of ligand in increasing order of their crystal field splitting value
(from weak to strong field ligand) is known as spectrochemical series.
 Bonding in Coordination Compounds

Isolated
transition metal
atom Bonded
transition metal
atom
Crystal field splitting ( D) is the energy difference between
two sets of d orbitals in a metal atom when ligands are present

22.5
 High Spin and Low Spin Complex

According to crystal field theory, a complex can be classified as high spin or low spin. When talking about
all the molecular geometries, we compare the crystal field splitting energy Δ and the pairing energy ( P ).
Normally, these two quantities determine whether a certain field is low spin or high spin.

When crystal field splitting energy is greater than the pairing energy( ∆o > P), electrons will fill up all the
lower energy orbitals first and only then pair with electrons in these orbitals before moving to the
higher energy orbitals. Electrons tend to fall in the lowest possible energy state, and since the pairing
energy is lower than the crystal field splitting energy, it is more energetically favorable for the electrons
to pair up and completely fill up the low energy orbitals until there is no room left at all, and only then
begin to fill the high energy orbitals. [ Low spin complex]

On the other hand, when the pairing energy is greater than the crystal field energy ( ∆o < P), the electrons
will occupy all the orbitals first and then pair up, without regard to the energy of the orbitals.
If every orbital of a lower energy had one electron, and the orbitals of the next higher energy
had none, an electron in this case would occupy the higher energy orbital. [ High spin complex]
For d4 ions, The fourth electron can either pair up in t2g
orbital or it can enter to eg orbital. It depends on crystal field
splitting, Δo value and pairing energy (P).

If Δo < P, electrons enters eg orbitals giving configuration

t2g3 eg1. These ligands are weak field ligands and form high
spin complexes.

If Δo > P, fourth electron pair up on t2g and the configuration

becomes t2g4 eg0. These ligands are strong field ligands and
form low spin complexes.

What are the possible reasons for transition metal compounds

to be coloured?
 Bonding in Coordination Compounds
Write the electronic configuration for d4 , d5 and d6 configuration
according to t2g and eg sets when o > P and o < P.

o<P o>P

22.5
Colour of metal complexes:
The absorption maximum for the complex ion
[Co(NH3)6]3+ occurs at 470 nm. What is the color of
the complex?

Absorbs blue ( f= 479 nm ) ,

Will appear orange.

22.5
Strong ligand
= large splitting
= large
absorption
Non coloured compounds of d- block metals

Zinc with the electronic structure [Ar] 3d104s2 doesn't count as a

transition metal whichever definition you use. In the metal, it has a full
3d level. When it forms an ion, the 4s electrons are lost - again leaving
a completely full 3d level.

At the other end of the row, scandium ( [Ar] 3d14s2 ) doesn't really
counts as a transition metal either. Although there is a partially filled d
level in the metal, when it forms its ion, it loses all three outer
electrons.

The Sc3+ ion doesn't count as a transition metal ion because its 3d level
is empty.
When white light is passed through a solution of this ion, some
of the energy in the light is used to promote an electron from
the lower set of orbitals i.e. t2g into a space in the upper set i.e
eg .
Colour
property

Metal complex absorbs light of certain frequency (say red)

region during d-d transition of electrons and transmits rest
of the light which is complementary colour the absobed
light( i.e. cyan or light blue)

Factor affecting colour of complex:

1. Nature of ligand
2. Oxidation state of central metal atom
3. Coordination no. of ion
Examples:
Bonding in Coordination Compounds

22.5