Coordination Compounds

Coordination Compounds are the backbone of modern inorganic and bio–inorganic chemistry and
chemical industry.

we learnt that the transition metals form a large number of complex compounds in which the metal
atoms are bound to a number of anions or neutral molecules.
In modern terminology such compounds are called coordination compounds.

Chlorophyll , hemoglobin and vitamin B12 are coordination compounds of magnesium, iron and
cobalt respectively.

Coordination compounds also find many applications in electroplating, textile dyeing and
medicinal chemistry.
 Werner’s Theory of Coordination Compounds
Alfred Werner (1866-1919), a Swiss chemist was the first to formulate his ideas about the
structures of coordination compounds.

Werner proposed the concept of a primary valence and a secondary valence for a metal ion.

Binary compounds such as CrCl3,CoCl2 or PdCl2 have primary valence of 3, 2 and 2 respectively.

In a series of compounds of cobalt(III) chloride with ammonia, it was found that some of the
chloride ions could be precipitated as AgCl on adding excess silver nitrate solution in cold but some
remained in solution.

Werner added the above four cobalt(III) complexes in table with an excess silver nitrate solution.
Which resulted in different amounts of silver chloride precipitate.
*He concluded that in CoCl3.6NH3, 3Cl– ions react with 3 silver ion form 3 silver chloride precipitates
which act as primary valency and 6NH3 molecules act as secondary valency. Thus in modern term
the compound is written as [Co(NH3)6] Cl3.

*Similarly, for CoCl3. 5NH3, 2Cl– ions act as primary valency, the remaining 1Cl– and 5NH3 ions act
as secondary valency. So the compound is [Co(NH3)3Cl] Cl2

*For CoCl3.4NH3, 1Cl– is primary valency, 2Cl– and 4NH3 is secondary valency. So the compound is
[Co(NH3)5 Cl2] Cl

*For CoCl3.3NH3, all 3Cl– and 3NH3 ion act as secondary valency So the compound is
[Co(NH3)5Cl3]

*He represents the primary valencies by dotted lines(…….) and secondary valencies by solid line (—)
Note that the last two compounds in Table 9.1 have identical empirical formula, CoCl3.4NH3, but
distinct properties. Such compounds are termed as isomers. Werner in 1898, propounded his
theory of coordination compounds. The main postulates are:
1. In coordination compounds metals show two types of linkages
(valences)-primary and secondary.

2. The primary valences are normally ionisable and are satisfied by

negative ions.

3. The secondary valences are non ionisable. These are satisfied by

neutral molecules or negative ions. The secondary valence is equal to
the coordination number and is fixed for a metal.

4. The ions/groups bound by the secondary linkages to the metal have

characteristic spatial arrangements corresponding to different
coordination numbers.
 Evidence in favour of Werner’s theory

1. Cryoscopic Measurement:
The cryoscopic measurement (i.e., measurement of depression in freezing point) gives the number of
ions formed by the dissociation of an ionic compound. The depression in freezing point is a
colligative property and depends upon the number of particles in the solution. The greater the
number of particles, the more will be the freezing point.
2. Electrical Conductance Measurement:
The conductance of solution depends upon the numbers of charge particles
present in that solution.
Limitation of Werner’s theory:-
*Though Werner explained some properties of the coordination compound,
he failed to explain the colour of the coordinate compound.

*He could not explain the magnetic and optical properties of coordination
compounds.

*He could not answer the question, why does the coordination sphere have a
definite geometry.

Heteroleptic Complex
Heteroleptic complexes: Heteroleptic complexes are those in which a metal ion is
surrounded by more than one type of ligand. Heteroleptic complexes are those in which the
metal atom or ion is connected to more than one type of ligand. These are complexes in
which a metal is bonded solely by ore-type ligands, such as [Co(NH3)6]3+ Complexes
heteroleptic: These are complexes in which a metal is bound by multiple types of ligands,
such as [Co(NH3)4]Cl2]+.
DEFINITIONS OF SOME IMPORTANT TERMS
PERTAINING TO COORDINATION COMPOUNDS
Coordination Entity and Counter Ion

A coordination entity constitutes a central metal atom or ion bonded to a fixed number of ions or
molecules. It is enclosed in square bracket and is collectively termed as the coordination sphere.

For example, [CoCl3(NH3)3 is a coordination entity in which The cobalt ion is surrounded by three
ammonia molecules and three chloride ions

The ionisable groups are written outside the bracket are called counter ions. It is also known as
spectator ion.
Central Atom/Ion
In a coordination entity, the atom/ion to which a fixed number of ions/groups
are bound in a definite geometrical arrangement around it, is called the
central atom or ion.

For example, the central atom/ion in the coordination entities: [NiCl2(H2O)4],

[CoCl(NH3)5]2+ and [Fe(CN)6]3– are Ni2+, Co3+
and Fe3+, respectively. These central atoms/ions are also referred to as Lewis
acids.

Ligands
An ion or a molecule which can donate pair of electrons to a metal atom or a
metal ion and can form dative bond is called ligand. These may be simple ions
such as Cl–, small molecules such as H2O or NH3, larger molecules such as
H2NCH2CH2NH2 or even macromolecules, such as proteins.
On the Basis of Denticity:
Denticity is the number of coordinate bonds formed by
one ligand.
1. Monodentate
2. Bidentate
3. Polydentate
4. Flexidentate
5. Ambidentate
Bidentate/Di dentate Ligands
Flexidentate Ligand
A polydentate ligand which is found to have different denticity in different
coordination compounds is called a flexidentate ligand.
Note that in a particular complex, denticity of a particular ligand is fixed, it can
not be flexible in the same compound.
EDTA can act as hexa, penta as well as tetra dentate ligand.
For example;
EDTA usually acts as hexadentate ligand but in [Cr(II)(OH)(EDTA)]2– and
[Co(II)Br(EDTA)]2– as pentadentate and in[Pd(IV)H2(EDTA)]0 as a tetradentate
ligand.
Sulphate ion, SO42– can also be mono or bidentate
ligand.
For example;
Ambidentate Ligand
Ligands which can ligate through two different atoms present in it are
called ambidentate ligands. Examples are NO2– and SCN– ions. NO2–
ion can coordinate through either the nitrogen or the oxygen atoms to a
central metal atom/ion. Similarly, SCN– ion can coordinate through the
sulphur or nitrogen atom. Such possibilities give rise to linkage
isomerism in coordination compounds.
For examples:
 Chelation and Denticity
When coordination of more than one sigma-electron pair donor group from
the ligand to the same central atom/ion takes place, it is called chelation,
and the ligand known as chelating ligand. The number of such sigma bonds
by such a ligand indicate the denticity of the ligand. For example:
unidentate, didentate, terdentate or tridentate, tetradentate, etc.
Chelate Ligand
Chelate ligand is a di or polydentate ligand which uses its two or more donor atoms to bind
a single metal ion producing a ring. The complex formed is referred to as a chelate complex
and the process of chelate formation is called chelation.
Chelate rings may have any number of atoms; the most common contain five or six atoms,
including the metal ion. Smaller rings have angles and distances that lead to strain; larger
rings frequently result in crowding both within the ring and between adjoining ligands.
Some ligands can form more than one ring;
ethylenediaminetetracetate (EDTA) can form five by using four carboxylate groups and the
two amine nitrogens.
The chelate complexes are more stable than similar complexes containing unidentate ligands under similar
conditions. The greater stability of the chelate complex in comparison to normal complex
is called chelate effect. For example,

The five and six

membered rings are more
stable.
The following are types and examples of ligands on the basis of this classification.
 Tridentate/Terdentate Ligand/Chelation

Diethylenetriamine (dien) or[N-(2-aminoethyl)-1, 2-ethanediamine] is a terdentate

ligand.

In the coordination entity (Pt Cl(dien)]+, dien, [N-(2-aminoethyl)-1, 2-ethanediamine] isa terdentate ligand.
e
Example 3: Ethylene diamine is an example of a ______ ligand:
(1) Monodentate (2) Bidentate
(3) Tridentate (4) Hexadentate

Example 4: [EDTA]4– is a
(1) Monodentate ligand (2) Bidentate ligand
(3) Quadridentate ligand (4) Hexadentate ligand

Sol. (CH2COO–)2—N—CH2—CH2—N—(CH2COO–)2.
It is a hexadentate ligand.

5. Which of the following is a chelate ligand?

(1) Hydrazine (2) Oxalate
(3) Cyanide (4) Ammonia

6. Denticity of glycinato ligand is :-

(1) 1 (2) 2
(3) 3 (4) 4
Coordination Number
The coordination number (C.N) of a metal ion in a complex can be defined as the number of ligand donor atoms
to which the metal is directly bonded by sigma bonds.

The coordination number is generally 2, 4 (or) 6, occasionally 8 (in Osmium complexes).

It is equal to the number of monodentate ligands that are bound to central metal atom or ion through a dative
bonds.

Shape of the complex species depends on its coordination number.

Coordination Polyhedron
The spatial arrangement of the ligand atoms which are directly attached to the central atom/ion defines
a coordination polyhedron about the central atom. The most common coordination polyhedra are
octahedral, square planar and tetrahedral.
Oxidation Number of Central Atom/Ions
The oxidation number of the central atom in a complex is defined as the charge it would carry if
all the ligands are removed along with the electron pairs that are shared with the central atom.
The oxidation number is represented by a Roman numeral in parenthesis following the name of
the coordination entity.

Homoleptic and Heteroleptic Complex Compound

Homoleptic Complex
The complex in which the central metal atom (or) ion bound with only one kind of ligand.

Heteroleptic Complex
The complex in which the central metal atom (or) ion bound with more
than one kind of ligands.
Ex: [Co(NH3)5Cl]+2
Example 5: Explain why [Fe(en)3]3+ is less stable than
[Fe(EDTA)]–?
Sol. [Fe(en)3]3+ has three, five membered rings in the structure. On the other hand
[Fe(EDTA)]– has five membered ring in the structure.

As the number of rings in coordination compound increases, stability also increases due to chelation effect;
Hence, [Fe(en)3]3+ is less stable than [Fe(EDTA)]–
Example 6: Ligands are:
(1) Lewis acids (2) Lewis bases
(3) Neutral (4) None of these
Sol. Ligands are Lewis bases as they donate lone pair of electrons to the metal ion to form
coordinate covalent bonds.

Concept Application
7. Among the following which are ambidentate ligands?
(i) NO2¯ (ii) NO3¯ (iii) EDTA4– (iv) SCN¯
(v) H2NCH2CH2NH2
(1) (i) and (ii) (2) (iii) and (iv)
(3) (i) and (iv) (4) (iii)
8. Total number of possible pi-bonds in [Ag(CN)2]– is:
(1) 2 (2) 3
(3) 4 (4) 6
NOMENCLATURE OF COORDINATION COMPOUNDS

IUPAC Name of Coordination Compounds

In modern terminology, complex compounds are called Coordination
compounds . Theory of coordination compounds was explained by Werner.
Coordination entities are mainly of two types. They are
(a) Mononuclear Complexes Ex : K4[Fe(CN)6], [CrCl(H2O)5]Cl2
(b) Polynuclear Complexes/Bridged complex Ex : [Co2(NH3)6(OH)3]Cl3
Mono nuclear complex compounds are divided into three types:
1. Cationic Complexes: Those complexes in which coordination entity hold
positive charge are called cationic complexes . Some of the cation complexes
are:
[Co(NH3)6]Cl3 Hexaamminecobalt(III) chloride

[Pt(Cl)(NH3)5]Cl3 Pentaamminechloroplatinum (IV) chloride

[CrCl(NO2)(NH3)4]NO3 Tetraamminechloronitrochromium(III) nitrate

[Pt(NH3)6]Cl4 Hexaammineplatinum(IV) chloride.

[Co(NH3)4(H2O)Cl]Cl2 Tetraammineaquachlorocobalt(III) chloride.

2. Anionic Complexes: Those complexes in which coordination
entity hold negative charge are called anionic complexes.
Some of the anionic complexes are:

K4[Fe(CN)6] Potassium hexacyanoferrate(II)

Na2[ZnCl4] Sodium tetrachlorozincate(II)

K3[Fe(CN)5NO] Potassium pentacyanonitrosylferrate(II)

K3[Fe(CN)6] Potassium hexacyanoferrate(III)

K3[Cr(C2O4)3] Potassium trioxalatochromate(III)

K3[CoCl2(C2O4)2] Potassium dichlorodioxalatocobaltate(III)

K2[HgI4] Potassium tetraiodomercurate(II).

3. Neutral Complexes: Those complexes in which coordination sphere is neutral.
Some of the neutral complexes are:

[Co(NH3)3Cl3] Triamminetrichlorocobalt(III)

[Pt(NH3)2Br2Cl2] Diamminedibromodichloroplatinum(IV)

[Cr(H2O)3Cl3].3H2O Triaquatrichlorochromium(III)trihydrate
.
Fe(CO)5 Pentacarbonyliron(0)

[Co(NH3)3(NO2)3] Triamminetrinitrocobalt (III)

Rules for Writing the Formulae of Coordination Compounds

All mononuclear complex entities contain a single central metal atom, which
is symbolised first.

If more than one ligand of each type is present, alphabetical order according
to the first letter is to be followed in listing them .

Formula of polyatomic ligands are enclosed in parentheses . Complete

coordination entity is enclosed in square brackets.

Different species present in the formula are written continuously without

leaving space .

Charge of anionic or cationic complex is indicated outside the square

brackets as a right superscript.
 Order of Naming Ions
The positive ion is named first followed by the negative ion.
Ex: K4[Fe(CN)6] → 4K+ + [Fe(CN)6]4–
Potassium hexacyanoferrate (II)

Name of the non ionic (or) neutral complex must be written in one word.
Ex: [Ni(CO)4]- tetracarbonylnickel(0).
Naming the Coordination Entity
In naming the coordination entity, the ligands are named first and then central
metal ion.

Name of Ligands

Names of the neutral ligands should be written as it

is.

Ex: NH2 CH2 CH2 NH2- Ethylene diamine

C6H5N - Pyridine
PH3 - Phosphine
(C6H5)3P - Triphenylphosphine
However, there are a few exceptions in naming neutral ligands.
Ex:

H2O - Aqua

NO - Nitrosyl

NH3 - Ammine

CS - Thiocarbonyl

CO - Carbonyl

NS - Thionitrosyl
Name of the negative ligands must be ended with ‘o’. In general, if the
anionic ligand name ends in -ide, -ite or -ate, the terminal -e- is
replaced by ‘o’ giving -ido, -ito and -ato respectively.
Order of Naming Ligands:-
If the same complex compound contain different ligands, their names should be written in
alphabetical order.
Ex: [Pt(Br)(Cl)(NO2)(NH3)]– is named as
Amminebromochloronitroplatinate (II) ion.

Numerical Prefixes to Indicate Number of Ligands

If the number of a particular ligand is more than one in the complex ion, the number is indicated by di,
tri, tetra, penta etc.

Ex:
[Cr(NH3)6]Cl3 - Hexaamminechromium(III) chloride

[Ni(CN)4]2– Tetracyanonickelate(II)ion
If the same ligand can donate lone pairs from more than one center, they are named as bidentate, tridentate etc.,
depending on the number of lone pairs donated.
Ex: NH2CH2CH2NH2

The number of bidentate, tridentate etc. ligands is mentioned with bis, tris, tetrakis, etc. if they already contain di,
tri, tetra etc. in their names.
Ex: [PtBr2(NH2CH2CH2NH2)2]Cl2 is named as
dibromobis (1, 2-ethanediamine) platinum (IV) chloride.

Ending Names:-
When the complex is anionic, the name of the central metal atom ends with -ate.
For cationic and neutral complexes, the name of the metal is written without any characteristic ending.

Ex: Cationic complex: [Co(NH3)6]Cl3 - Hexamminecobalt(III) chloride

Ex: Neutral complex : [Ni(CO)4] - Tetracarbonylnickel(0)

Ex: Anionic complex : K[PtCl5(NH3)] -Potassium amminepentachloroplatinate(IV)

If the complex is anion, the name of the metal should be taken from Latin language.
Ex:
Cu - Cuprum – Cuprate Sn - Stannum - Stannate
Fe - Ferrum – Ferrate Pb - Plumbum – Plumbate
Ag - Argentum – Argentate Au - Aurum - Aurate
Cr - Chromium – Chromate Ni - Nickel - Nickelate
Oxidation State of Central Metal ion
The oxidation state of the central metal ion is designated by a Roman numerical (such as II, III, IV) in the brackets at the
end of the name of the complex without a gap between the two.

Ex: [CoCl(NH3)5]Cl2 - Pentaamminechlorocobalt(III) chloride.

Point of Attachment
When a ligand can coordinate through more than one atom, then the point of attachment of the ligand is indicated by
putting the symbol of the atom through which coordination occurs, after the name of the ligand.
Sometimes, different names are used for alternative modes of attachment.
Ex: NO2
– can coordinate through -N (or) -O. If it co-ordinates through N, it is called nitrito -N (or simply as nitro).
On the other hand, if it coordinates through -O, (-ONO-), it is called nitrito-O

–NO2– (through N) Nitrito -N (or) –ONO– (through -O) Nitrito-O

–SCN– (through -S)- –NCS– (through -N)

Thiocyanato (or) isothiocyanato
Or thiocyanato-S or thiocyanato-N
Example 7: Write IUPAC names of the following
(1) Na2[Fe(CN)5NO+] (2)[Co(NH3)4Cl(NCS)]+
(3) K4[FeO4] (4) K2[Co(N3)4]

Sol. According to IUPAC nomenclature, the IUPAC names are as follows:

(1) Sodium pentacyanonitrosoniumferrate(II)
(2) Tetraamminechloridothiocyanato-N-cobalt(III)ion
(3) Potassium tetraoxidoferrate(IV)
(4) Potassium tetraazidocobaltate(II); N3¯ is azide.

Example 8: Write the structural formula corresponding to

each of the following IUPAC names:
(1) Tetraamminedichoridocobalt(III) chloride
(2) Dicyanidoargentate(I) ion
(3) Tris(ethane-1,2-diamine)copper(II) sulphate
(4) Sodium diaquatetrahydroxidoaluminate(III)

Sol. According to IUPAC nomenclature, the structural

formula are as follows:

(1) [Co(NH3)4Cl2]Cl (2) [Ag(CN)2]¯

(3) [Cu(en)3]SO4 (4) Na[Al(H2O)2(OH)4]
7. IUPAC name of [Pt(NH3)3(Br)(NO2)Cl]Cl is:-

(1) Triamminechlorobromonitroplatinum(IV) chloride.

(2) Triamminebromonitrochloroplatinum(IV) chloride.

(3) Triamminebromochloronitroplatinum(IV) chloride

.
(4) Triamminenitrochlorobromoplatinum(IV) chloride.

8. The IUPAC name of [Ni(NH3)4] [NiCl4] is:-

(1) Tetrachloronickel(II) tetraamminenickel(II)

(2) Tetraamminenickel(II) tetrachloronickel(II)

(3) Tetraamminenickel(II) tetrachloronickelate(II)

(4) Tetraaminenickel(II) tetrachloridonickelate(IV)

 [Cr(NH3)3(H2O)3]Cl3
is named as:- triamminetriaquachromium(III) chloride

[Co(H2NCH2CH2NH2)3]2(SO4)3
is named as:- tris(ethane-1,2–diammine)cobalt(III) sulphate

[Ag(NH3)2][Ag(CN)2]
is named as:- diamminesilver(I) dicyanoargentate(I)
 (iv)The formula corresponding to the IUPAC name
amminebromidochloridonitrito-N-platinate(II)
is
[Pt(NH3)BrCl(NO2)]−

(v) [PtCl2(en)2](NO3)2]
.

(ii)The formula of the coordination compound

Potassium tetracyanonickelate(II) is
K2[Ni(CN)4]
Tetracyano means 4 CN groups.

(iii)The formula of the given compound

Tris(ethane-1,2-diamine) chromium(III) chloride is
[Cr(en)3]Cl3
ISOMERISM IN COORDINATION
COMPOUNDS
When complex compounds have same molecular formula but have different structural or
spatial arrangement of ligand around central metal atom/ion called as isomers and this
phenomenon is known as isomerism.

Co-ordination compounds exhibit isomerism. The isomerism can be divided into two types. They are
(1) Structural isomerism
(2) Stereoisomerism

(1) Structural Isomerism:-This isomerism arises due to the difference in the structures of complexes.

It is of four types:
(i) Ionisation Isomerism: Complexes which have the same molecular formula but give different ions in solution are
called ionisation isomers and the phenomenon is called ionisation isomerism.
Ex:
[Co(NH3)5SO4]Br and [Co(NH3)5Br]SO4 Ionisation isomers are formed by the interchange of the
position of ligands inside (or) outside the coordination sphere.

Ionisation isomerism arises, when the counter ions in a complex compound can also function as ligands.
The following pairs of compounds give different ions in solutions.
[Co(NO3)(NH3)5]SO4 gives sulphate ions
while [Co(SO4)(NH3)5](NO3) gives nitrate ions.