����������������������������������������������������������������������

Nomenclature of Coordination Compounds  

Coordination compounds are named according to the rules suggested by International Union of Pure and Applied Chemistry (IUPAC)
in 1976. These rules are as follows.
i. The order of naming of cations and anions of complex compound.
       a.                                    If a compound is ionic, i.e. if a complex compound is composed of cation and anion, the
name of the cation is mentioned first and then the name of the anion is written. For example:
         �                                                            In naming of complex K2[PtCl6], the name of the cation, i.e. K
+

is written first followed by the name of the anion, i.e. [PtCl6]2–.

         �                                                            In
naming of complex [Co(NH3)5Cl]Cl2, the name of the cation,
i.e. [Co(NH3)5Cl]  is written first followed by the name of the anion, i.e. Cl–.
naming of complex [Pt(NH3)4Cl2]2+ [PtCl4]2–, the name of
         �                                                            In
the cation, i.e.
[Pt(NH3)4Cl2]2+ is written first followed by the name of anion [PtCl4]2–.
       b.                                    If the complex compound is neutral (non-ionic), the name of the complex compound is

written as one word. Thus, the name of [Pt(NH3)4Cl2]o is written as one word.

ii. How to name the species present in coordination sphere?

In naming the species present in coordination sphere, the ligands are named first followed by the name of the
central metal atom.

iii. What is the order of naming ligands?

If the coordination sphere of a given complex compound contains various types of ligands, these ligands are named
in alphabetical order. For example, in the naming of the complex [Co(NH3)4Cl(NO2)]+ ion, the ligands are named in
the order ammine followed by chloro which is followed by nitro.

iv. How to name ligands?

       a.                                    The names of negative ligands end in ‘o’. For example:
F– fluro

Cl– chloro

H– hydro or hydrido

O2– oxo
       b.                                    Neutral ligands have no special ending. For example:
CO carbonyl
NO nitrosyl
CS thiocarbonyl
H2O aquo or aqua
NH3 ammine
       c.                                    The name of positive ligands end in ‘ium’. For example:
NO2+ nitronium

NO+ nitrosonium

NH2 – NH3+ hydrazinium

H3O+ hydronium

NH4+ ammonium
       d.                                    Organic
free radicals are given their own names. These are supposed to be neutral species,
i.e. they do not contain any charge on them. Examples of some free radicals are given below.

CH3 methyl
C6H5 phenyl
C2H5 ethyl
C5H5 cyclopentadienyl
C5H5N pyridine (py)
P(C6H5)3 triphenylphosphine
H2NCSNH2 thiourea
H2NCH2CH2NH2 ethylenediamine (en)

v. How to indicate the number of ligands?

a complex contains two or more than two simple ligands of the same type (such as Cl–,
       a.                                    If

Br–, NO2–, C2O42–, NH3, H2O, etc), their numbers are indicated by putting the following prefixes before
the name of ligand.
         �                                                            di (for two ligands)
         �                                                            tri (for three ligands)
         �                                                            tetra (for four ligands)
         �                                                            penta (for five ligands)
         �                                                            hexa (for six ligands)
         �                                                            hepta (for seven ligands)
         �                                                            octa (for eight ligands)
         �                                                            nona (for nine ligands)
         �                                                            deca (for ten ligands)
�
          �                                                            undeca (for eleven ligands)
         �                                                            dodeca (for twelve ligands)
       b.                                    If a complex contains two or more than two polydentate ligands or organic molecules, their
numbers are indicated by putting the following prefixes before the name of ligand.
         �                                                            bis (for two ligands)
         �                                                            tris (for three ligands)
         �                                                            tetrakis (for four ligands)
         �                                                            pentakis (for five ligands)
         �                                                            hexakis (for six ligands)

vi. How to name the bridging ligand?

If a complex has bridging ligands, the prefix ‘- -‘ is used before the name of each of the ligands. For example, the
name of complex  is written as pentamminecobalt(III)- -
amidotetrammineaquocobalt(III) chloride. If a complex has two similar bridging ligands, -di is used for its name.
For example, the name of complex

is written tetraaquairon(III)- -dihydroxotetraaquairon(III) sulphate or octaaqua- -di-hydroxodiiron(III) sulphate or di-

-hydroxobis(tetraaquairon(III)) sulphate.

vii. How to name ambidentate ligands?

A unidentate ligand such as SCN–, ONO– which contains more than one coordinating atom is called
ambidentate ligand.

In such ligands, the point of attachment of the ligand to the central metal atom is indicated by placing the symbol of
the donor atom attached after the name of the group. In some cases, different names may be used for alternative
modes of attachment. For example, thiocynate can coordinate through either N or S as:

SCN– thiocyanato (coordination through S-atom)

NCS– isothiocyanato (coordination through N-atom)

 Similarly, NO2 can coordinate through either N or O.

NO2– nitro (coordination through N-atom)

ONO– nitrito (coordination through O-atom)

�

viii. How to name the central metal atom?

In order to name the central metal atom, the following two cases arise.
       a.                                    If the coordination sphere of the complex compound has negative charge, the name
of the central metal atom ends in ‘ate’ and the oxidation state of the metal (whether positive,
negative or zero) is written in Roman numerals (such as 0, I, II, III … - I, -II, -III, etc) in bracket at
the end of the name of the metal atom. The names of some metals are given.
       b.                                    If the coordination sphere of the complex compound has positive charge or is
neutral, the name of the central metal atom remains as such and the oxidation state of the metal
is written in Roman numerals in bracket at the end of the name of the metal atom.

ix. How to name stereoisomers?

Geometrical isomers named by the term ‘cis’  is to denote similar groups at adjacent positions and ‘trans’  similar
groups at opposite position. Optically active compounds are designated by the symbol (+) or d and (–) or l for dextro
and laevo rotatory compounds, respectively.

Some examples illustrating the nomenclature of complexes:

K[Ag(CN)2] Potassium dicyanoargentate(I)
K[BF4] Potassium tetrafluoroborate(III)
[Ni(CO)4]  tetracarbonylnickel(0)
[Co(H2O)6] Cl2 hexaaquacobalt(II) chloride

[Mn(H2O)6]2+ hexaaquamanganese(II) ion

[Cr(C6H6)2] bis(benzene)chromium(0)
[Fe(C5H5)2] bis(cyclopentadienyl)iron(II)
K2[Ni(EDTA)] Potassium ethylenediamminetetracetatonickelate(II)
chlorotriphenylphosphinepalladium(II)- -dichloro
chlorotriphenylphosphinepalladium(II)
or
di- -chlorobis(chlorotriphenylphosphinepalladium(II))

Na2[CrOF4] Sodium tetrafluorooxochoromate(IV)

[Co(CO)4]– tetracarbonylcobaltate(–I)

[Ag(NH3)2]+ diamminesilver(I) ion

 trans - diamminedichloroplatinum(II)
 Board questions
1. Write the names of the following complexes using IUAC name.
(i) [Co(NH3)6]3+
(ii) [Fe(CN)6]4–
(iii) K3[Cr(C2O4)2]
(iv) [Co(en)2(ONO)Cl]Cl CBSE 1997 (Outside Delhi), 2 marks
2. Write the formula of tetrachlorocuprate(II) ion. CBSE 1997 (Delhi), 1mark
Quest Tutorials
Head Office : E-16/289, Sector-8, Rohini, New Delhi. Ph. 65395439