Consider the following coordination compound

[Co(H2O)Cl(en)2]Cl2
Here,

Co (Cobalt) : is the central metal atom/ion

(en)2, (H2O), (Cl) are neutral didentate, neutral unidentate and anionic unidentate ligands
respectively.

Ligands and central metal atom/ion are bonded through coordinate bonds to from coordination
sphere, which is enclosed within square brackets.

Coordination number of a metal atom is number of bonds between metal and ligands. e.g.,
in [Co(en)2(H2O)Cl]Cl2, coordination number of Co is six.

Cl is a counter ion which is outside the coordination sphere.

IUPAC Nomenclature of Coordination Compounds

(i)
(ii)

Name of the cation is written before the name of the anion.

Within a complex ion or coordination entity, names of ligands are cited before the metal
atom/ion.

(iii)

Identical ligands are represented by prefixing di, tri, tetra etc. to their name.

(iv)

Different ligands are reported in alphabetical order.

(v)

(vi)

When the name of ligands includes a numerical prefix like mono or di. Their total number
is represented by prefixing bis for di, tris for tri, tetrakis for tetra and so on and the ligand
to which it refers is enclosed in parenthesis.
Name of anionic ligand ends in o
Cl = Chlorido

Br = Bromido

C2O42 = Oxalato

H = Hydrido

CN = Cyanido
(vii)

EDTA4 = Ethylenediaminetetracetato

The names of neutral and cationic ligands are the same except NH3(ammine), CH3NH2
(methylamine/methanamine), H 2O (aqua), CO (carbonyl), NO (nitrosyl) and

CH2

NH2

CH2

NH2

(ethylenediamine/ethane-1,2-diamine).

85

Chemistry

(viii)

When the charge on coordination complex is negative name of central metal atom/ion ends
in ate.
Iron (ferrum) Ferrate

Cobalt = Cobaltate

Silver (argentum) argentate

Nickel = Nickelate

Gold (aurum) aurate

(ix)
(x)

Oxidation state of metal atom is expressed in Roman numeral and is written following its
name and enclosed in parenthesis.
Name of coordinate entity is a single word.
For e.g. [Co(H2O) Cl(en)2] Cl2 will be named as aquachloridobis (ethane-1, 2-diamine) cobalt
(III) chloride.

Isomerism in Coordination Compounds

(i)

Ionization Isomerism : This isomerism results when compounds with same molecular
formula give different ions in the solution e.g., {Co (NH3)5Br]2+ SO42 and [Co(NH3)5(SO4)]+
Br. Here counter ion itself is a potential ligand.

(ii)

Solvate Isomerism : It arises when H2O molecule acting as ligand becomes water of
hydration outside the coordination sphere, i.e., here water forms a part of the coordination
entity or is outside it. For example, there are three hydrate isomers of CrCl 3.6H2O as shown
below :
[Cr(H2O)6]Cl3, [Cr(H2O)5Cl] Cl2.H2O, and [Cr(H2O)4Cl2] Cl.2H2O.

(iii)

Linkage Isomerism : This isomerism results when a ligand attaches with central atom/
ion in two different ways. Some common examples of such ligands are : nitritoN(NO2)
and nitritoN(ONO), cyano (CN) and isocyano (NC), thiocyanato (SCN), and
isothiocyanato (NCS), cyanato (OCN) and isocyanato (NCO).
Some example of linkage isomers are : [Co(NO 2) (NH3)5]Cl2 and [Co(ONO)(NH3)5]Cl2;
[Cr(H2O)5(SCN)]2+ and [Cr(H2O)5 (NCS)]2+

(iv)

Coordination Isomerism : This type of isomerism is shown by compounds in which both

cation as well as anion are complexes (coordination entities) and ligands may interchange
their position between the two complex ions. For example,
[CO(NH3)6] [Cr(C2O4)3] and [Cr(NH3)6] [Co(C2O4)3]

(v)

Geometrical Isomerism
(a)

Isomerism in complexes with coordination number 4 : Tetrahedral complexes

do not show geometrical isomerism because the relative position of the ligands with
respect to each other will be the same. The square planar complexes of the type
MA2X2, MA2XY, MA2BX and MABXY show this kind of isomerism, e.g., [Pt(NH3)2Cl2].

(b)

Isomerism in complexes with coordination number 6 : Octahedral complexes

of the type : MA4X2, MA3X3, MA4XY exist as cis-and trans-isomers. Common examples
are : [Co(NH3)4Cl2], [Co(NH3)4Cl(NO2)]

86

Chemistry

Complexes of the type : [M(AA) 2X2] and [M(AA)2XY] also show cis-trans isomers
(Here (AA) refers to symmetrical bidentate ligands and X and Y refer to anionic
ligands. Common examples are : [Co(en)2 Cl2]+, [Ni(OX)2Cl2]+ etc.
(ii)

Optical Isomerism : Chiral molecules i.e., molecules which do not have plane of symmetry,
exhibit optical isomerism. The optically active isomers called enantiomers or enantiomorphs
are non superimposable on mirror images of each other and rotate the plane of polarised
light equally but in opposite directions.
If the substance rotates the light to the right, i.e., in clockwise direction, it is dextrorotatory
or the d- form or (+) form. If the light is rotated in the anti-clockwise direction, the substance
is said to be levorotatory or l- form or () form. The optical isomers of a compound have
identical physical and chemical properties.
(b)

Isomerism in complexes with coordination number 6 : Octahedral complexes of

the type [M(AA)X2Y2], [M(AA) 2X2] and [M(AA)2XY] where (AA) is symmetrical
bidentate ligand and X and Y are monodentate ligands, can be resolved into a pair
of enantiomers. As seen earlier, the complexes of these types show geometrical
isomerism i.e., exist as cis-and trans-isomers. The trans isomer does not show optical
isomerism since it is symmetrical while only cis-isomer show optical activity as it is
unsymmetrical. Thus total three isomers may be possible in such cases.

Some common examples of the above type of complexes are :

[CO(en)(NH3)2Cl2]+, [Co(en)2Cl2]+
(ii)

Valence bond theory (VBT) : This theory, put forward by Linus Pauling (1931), is used
to explain the shapes of complexes and relation between the observed magnetic behaviour
and the bond type. It involves the hybridization of empty non equivalent orbitals of the
metal atom/ion, each of which then can accept a lone pair of electrons donated by the
ligands. The shape is octahedral, tetrahedral, square, planar, trigonal bipyramidal (or square
pyramidal) or linear when hybridization is d2sp3, sp3, dsp2, dsp3 or sp respectively.

87

Chemistry

Complexes of some transition metal ions/atoms on the basis of V.B. Theory.

Complex

Metal
Ion

[V(H2O)63]+

V3+

Cr(NH3)63+
Mn(CN)63
Fe(CN)63
Fe(CN)64
[FeF6]3
[Co(NH3)6]3+
[CoF6]3
[Ni(CN)4]2

Cr3+
Mn3+
Fe3+
Fe2+
Fe3+
Co3+
Co3+
Ni2+

Electron distribution
3s
3p
3d
2
2
2
2
2
2
2
2
2

Type of
Hybridisation

No. of
unpaired

d2sp3

d2sp3

4(le

d2sp3

pair up)

d2sp3

pair up)

d2sp3

sp3d2

d2sp3

sp3d2

dsp 2

sp3

sp

dsp2

6
6
6
6
6
6

4s

4p

4d

pairs up)

(2e

(2e

5
6

(2e

[pair up)

6
8

(1e

pairs up)

[Ni(CO)4]

Ni

[Cu(NH3)2]+
[Cu(NH3)4]2+

Cu+

10

Cu2+

8
0
1
(1e promoted to 4p)

[Cu(CN)4]3

Cu+

10

sp3

[Zn(NH3)4]2+

Zn2+

10

sp3

(iii)

2 (Jump to 3d)
0

Crystal Field Theory (CFT) : Crystal field theory is based on the assumption that the
metal ion and the ligands act as point charges and the interaction between them is purely
electrostatic, i.e., metal-ligands bonds are 100% ionic. The five d-orbitals is an isolated
gaseous metal atom/ion are degenerate. This degeneracy is maintained in a spherically
symmetrical field of negative charges.
However, when this negative field is due to real ligands in a complex, the degeneracy of the
d-orbitals is lifted due to asymmetrical field. This results in splitting of the d-orbital energies.
The pattern of splitting depends upon (a) nature of the crystal field such as octahedral,
tetrahedral of square planar and (b) basic strength of ligands.
Crystal field effects in octahedral coordination entities : In an octahedral complex,
the six ligands approach the central metal atom lying at the origin symmetrical along the

dx2 y2 , dz2 (eg)

0.6 0

Energy

1.

0 or 10Dq
0.4 0

d-orbitals in free ion

Average energy of
dxy, dyz, dxz (t2g )
d-orbitals in spherical Splitting of d-orbitals in
crystal field
an octahedral crystal field

Splitting of five d-orbitals in an octahedral crystal field.

88

Chemistry

cartesian axes. Initially, there is an increase in the energy of d-orbitals relative to that of
the free ion (just like that in a spherical field). Next, the orbitals lying along the axes (dxy,
dyz and dxz) which are lowered in energy relative to the average energy in the spherical
crystal field as shown below :
This splitting of five degenerate d-orbitals of the metal ion into two sets of d-orbitals with
different energies is called crystal field splitting. The two sets of d orbitals, i.e., dx 2 y2 and dz 2
and dxy , dyz and dzx are commonly called eg and t2g orbitals respectively. The crystal field splitting
is the energy difference between t2g and eg orbitals and is frequently measured in terms of a
parameter 0 where the subscript (0) stands for octahedral. (This is also measured in terms of
another parameter called Dq. The magnitude of splitting is arbitrarily fixed at 10Dq so that
(0 = 10Dq). The above energy level diagram shows that an electron will prefer to go into more
stable t2g orbital is stabilized by 0.40 (4Dq) energy while each electron occupying the eg orbital
shall be destabilized by an amount 0.60(6Dq) energy. This gain in energy achieved by preferential
filling of stable t2g orbitals over the energy of a randomly filled d-orbital is called the crystal field
stabilization energy (CFSE).
The net CFSE is equal to (6x 4y) Dq where x and y are the number of electrons in eg and
t2g orbitals respectively. The actual configuration adopted is decided by the relative value of 0 and
P (where P is the pairing energy). The energy required to cause pairing of electrons in the same
orbital is called pairing energy. If 0 < P, we have a weak field and high spin or spin free complex
and the fourth electron will enter one of the eg orbitals giving the configuration t2g3eg1. If now a fifth
electron is added to a weak field coordination entitity, the configuration becomes t2g3e2g. The
pairing of electrons will take place only if the gain in stability in terms of 0 is large enough to
overcome the loss in stability due to electron pairing. When 0 > P, we have a strong field and low
spin or spin paired complex and pairing will occur in the t2g level with eg level remaining unoccupied
in d1 to d6 systems.

89

Chemistry