SVKCHEM SURANA INDEPENDENT PU COLLEGE

II PU CHEMISTRY
UNIT-05: COORDINATION COMPOUNDS SVKCHEM

Introduction
The compounds in which metal atoms/ions are bonded to a number of anions or neutral
molecules are called coordination compounds.
The functioning of vital coordination compounds such as chlorophyll[Mg], haemoglobin[Fe],
vitamin-B12[Co]

Double salts and coordination compounds

When solution of two simple salts are mixed in stoichiometric proportions, concentration
and cooled, new crystalline compounds are formed. These are of two types,
(1) Double salts
(2) coordination or complex compounds

1. Double salts:
A salt that is formed by the combination of two simple salts and which ionise to give more
than two types of simple ions in the solution is called a double salt.
Examples:
Carnalite: KCI. MgCl2.6H2O
It ionizes in water as K + , Mg 2+ , Cl− . This solution answers to the tests for K + , Mg 2+ and Cl− .

Potash alum: K2SO4.Al2(SO4)3.24H2O

It ionizes in water as K + , Al3+ & SO2−
4 this solution answers to the tests for K , Al
+ 3+
& SO2−
4

2. Co-ordination or complex compounds:

The compound in which metal atom/ion is bonded to ions or neutral molecules (ligands)
through coordinate covalent bonds is called a coordination compound.
The co-ordination compounds when dissolved in water may or may not ionize. If they
ionise, they produce complex ions and simple ions.
Examples:
[Cu(NH3)4]SO4 → [Cu(NH3)4]2+ + SO2−
4
K2[PtF6] → 2K + [PtF6]
+ 2-

[Co(NH3)6][Cr(CN)6] → [Co(NH3)6]3+ + [Cr(CN)6]3-

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.
 He prepared and characterised a large number of coordination compounds and studied their
physical and chemical behaviour by simple experimental techniques.
 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.

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  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.
1 mol CoCl3.6NH3 (Yellow) gave 3 mol AgCl
1 mol CoCl3.5NH3 (Purple) gave 2 mol AgCl
1 mol CoCl3.4NH3 (Green) gave 1 mol AgCl
1 mol CoCl3.4NH3 (Violet) gave 1 mol AgCl

These observations, together with the results of conductivity measurements in solution can
be explained if (i) six groups in all, either chloride ions or ammonia molecules or both,
remain bonded to the cobalt ion during the reaction and (ii) the compounds are formulated
as shown in Table, where the atoms within the square brackets form a single entity which
does not dissociate under the reaction conditions. Werner proposed the term secondary
valence for the number of groups bound directly to the metal ion; in each of these
examples the secondary valences are six.

Formulation of Cobalt(III) Chloride-Ammonia Complexes

Solution conductivity
Colour Formula
corresponds to
Yellow [Co(NH3)6]3+ 3Cl− 1:3 electrolyte
Purple [CoCl(NH3)5]2+ 2Cl− 1:2 electrolyte
Green [CoCl2(NH3)4]+ Cl− 1:1 electrolyte
Violet [CoCl2(NH3)4]+ Cl− 1:1 electrolyte

Note that the last two compounds in Table 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.
4. The secondary valence is equal to the coordination number and is fixed for a metal.
5. The ions/groups bound by the secondary linkages to the metal have characteristic spatial
arrangements corresponding to different coordination numbers.

In modern formulations, such spatial arrangements are called coordination polyhedra. The
species within the square bracket are coordination entities or complexes and the ions outside
the square bracket are called counter ions. He further postulated that octahedral, tetrahedral
and square planar geometrical shapes are more common in coordination compounds of
transition metals. Thus, [Co(NH3)6]3+, [CoCl(NH3)5]2+ and [CoCl2(NH3)4]+ are octahedral
entities, while [Ni(CO)4] and [PtCl4]2– are tetrahedral and square planar, respectively.

Definitions of Some Important Terms Pertaining to Coordination Compounds

(a) Coordination entity
A coordination entity constitutes a central metal atom or ion bonded to a fixed number of
ions or molecules.
Ex: [CoCl3(NH3)3] is a coordination entity in which the cobalt ion is surrounded by three
ammonia molecules and three chloride ions.
Other examples are [Ni(CO)4], [PtCl2(NH3)2], [Fe(CN)6]4–, [Co(NH3)6]3+ .
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(b) Central atom/ion:
It is an electron pair(s) acceptor atom or ion containing vacant orbital to which a fixed
number of ligands are attached through co-ordinate bonds in definite geometrical
arrangements.
Ex: the central atom/ion in the coordination entities: [NiCl 2(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.

(c) Coordination sphere

The central atom/ion and the ligands attached to it are enclosed in square bracket and is
collectively termed as the coordination sphere. The ionisable groups are written outside the
bracket and are called counter ions.
Ex: K4[Fe(CN)6], the coordination sphere is [Fe(CN)6]4– and the counter ion is K+.

(d) Ligands
The ions or molecules having one or more donor atoms and each donate a pair of electrons
to the central metal atom or ion to form coordinate bond are called ligands.
Ligands are Lewis bases These may be simple ions such as Cl–, small molecules such as H2O or
NH3, larger molecules such as H2NCH2CH2NH2, EDTA or even macromolecules, such as
proteins. In rare cases some positive ions acts as ligands ( +NO)

Ligands are classified in terms of their donor atoms.

(i) Monodentate/ unidentate ligands: When a ligand is bound to a metal ion through a single
donor atom
Ex: Cl-, H2O, NH3 etc

(ii) Didentate:
When a ligand can bind through two donor atoms.
Ex: H2NCH2CH2NH2 (ethane-1,2-diamine) or
C2O4 2– (oxalate).

(iii) Polydentate: when several donor atoms are present

in a single ligand as N(CH2CH2NH2)3, the ligand is said to
be polydentate. Ethylenediaminetetraacetate ion (EDTA4–)
is an important hexadentate ligand. It can bind through
two nitrogen and 4 oxygen atoms to a central metal ion.

(iv)Ambidentate ligands:
The ligands which contain more than one donor atoms but
ligate through only one donor atom are called
ambidentate ligands.
Ex: NO2 – and SCN– ions. NO2– ion can coordinate either
through nitrogen or through oxygen to a central metal
atom/ion. Similarly, SCN– ion can coordinate through the
sulphur or nitrogen atom.

(v)Chelate ligand : When a di- or polydentate ligand uses its two or

more donor atoms to bind a single metal ion, it is said to be a chelate
ligand. The number of such ligating groups is called the denticity of the
ligand. Such complexes, called chelate complexes tend to be more
stable than similar complexes containing unidentate ligands.

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(e) Coordination number
The number of coordinate bonds between the ligands and central metal atom or ion of a
complex is called coordination number.
Ex: [PtCl6]2– and [Ni(NH3)4]2+, the coordination number of Pt and Ni are 6 & 4 respectively.
Similarly [Fe(C2O4)3]3– and [Co(en)3]3+, the coordination number of both, Fe and Co, is 6
because C2O42– and en (ethane-1,2-diamine) are didentate ligands.

(f) 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.
Ex: [Co(NH3)6]3+ is octahedral, [Ni(CO)4] is tetrahedral and [PtCl4]2– is square planar. the
shapes of different coordination polyhedra.

(g) Oxidation number of central atom

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.
Ex:oxidation number of copper in [Cu(CN)4]3– is +1 and it is written as Cu(I).

Types of Complexes
1. Homoleptic complexes
Complexes in which the metal atom or ion is linked to only one kind of donor atoms, are
called homoleptic complexes.
Ex: [Co(NH3)6]3+, [PtCl4]2- etc.

2. Heteroleptic complexes
Complexes in which the metal atom or ion is linked to more than one kind of donor atoms
are called heteroleptic complexes.
Ex: [Co(NH3)4Cl2]+, [CrSO4(NH3)5]+etc

Isomerism in Coordination Compounds

Two are more compounds having same molecular formula but different physical and
chemical properties are called Isomers and the phenomenon is called isomerism.
(a) Stereoisomerism
(i) Geometrical isomerism (ii) Optical isomerism

(b) Structural isomerism

(i) Linkage isomerism (ii) Coordination isomerism
(iii) Ionisation isomerism (iv) Solvate isomerism

Stereoisomerism
Stereoisomers have the same chemical formula and chemical bonds but they have different
spatial arrangement. These are of two types

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Geometric Isomerism
Geometrical isomers are of two types i.e., cis and trans isomers. This isomers is common in
complexes with coordination number 4 and 6.

Geometrical isomerism in complexes with coordination number 4

1. Tetrahedral complexes do not show geometrical isomerism.
2. Square planar complexes of formula [MX2L2] (X and L are unidentate) show geometrical
isomerism. The two X ligands may be arranged adjacent to each other in a cis isomer, or
opposite to each other in a trans isomer,
Ex: Pt(NH3)2Cl2

3. Square planar complex of the type [MABXL] (where A, B, X, L, are unidentate ligands)
shows three isomers, two cis and one trans.
Ex:[Pt(NH3)(Br)(Cl)(Py)].

Geometrical isomerism in complexes with coordination number 6

1. Octahedral complexes of formula [MX2L4], in which the two X ligands may be oriented cis
or trans to each other, Ex: [Co(NH3)4Cl2)]+.

2. Octahedral complexes of formula [MX2A2], where X are unidentate ligands and A are
bidentate ligand. form cis and trans isomers, Ex: [CoC12(en)2]

3. In octahedral complexes of formula [MA3X3], if three donor atoms of the same ligands
occupy adjacent positions at the corners of an octahedral face. it is known as facial (fac)
isomer, when the positions are around the meridian of the octahedron, it is known as
meridional (mer) isomer. Ex: [Co(NH3)3(NO2)3]

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(ii) Optical isomerism
These are the complexes which have chiral structures. It arises when mirror images cannot be
superimposed on one another. These mirror images are called enantiomers. The two forms
are called dextro (d) and laevo (l) forms.
Tetrahedral complexes with formula [M(AB) 2] show optical isomers and octahedral
complexes(cis form) exhibit optical isomerism.

Structural Isomerism
In this isomerism, Isomers have different bonding pattern. Different types of structural
isomers are
1. Linkage isomerism
Co-ordination compounds having same molecular formula but differ in the mode of
attachment of ambidentate ligands to the central metal ion.
Ex: [Co(NH3)5(NO2)]Cl and [Co(NH3)5(ONO)]Cl or pentaammine nitrito- N-Cobalt (III)
chloride and pentaammine nitrito-O-Cobalt (III) chloride.

2. Coordination isomerism
This type of isomerism arises from the interchange of ligands between cationic and anionic
complexes of different metal ions present in a complex,
Ex: [Cr(NH3)6) [CO(CN)6] and [CO(NH3)6] [Cr(CN)6]

3. Ionisation isomerism
Co-ordination compounds having same molecular formula but produces different ions when
dissolved in water.
Ex: [Co(NH3)5Br]SO4 and [Co(NH3)5(SO4)]Br

4. Solvate isomerism
Co-ordination compounds having same molecular formula but differ in the number of
molecules of solvent (water) as ligands.
Ex: the compounds with a molecular formula CoCl3. 6H20 can form three hydrate isomers as
follows,
[Co(H2O)6]CI3,
[Co(H2O)4C12]Cl·2H2O,
[Co(H2O)3Cl3]. 3H2O

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IUPAC Naming of Complex Compounds
Naming is based on set of rules given by IUPAC.

1. Name of the compound is written in two parts (i) name of cation, and (ii) name of anion.
2. The cation is named first in both positively and negatively charged coordination complexes.
3. The dissimilar ligands are named in an alphabetical order before the name of central metal
atom or ion.
4. For more then one similar ligands. the prefixes di, tri, tetra, etc are added before its name. If
the di, tri, etc already appear in the complex then bis, tris, tetrakis are used.
5. If the complex part is anion, the name of the central metal ends with suffix ‘ate’
6. Names of the anionic ligands end in ‘0’, names of positive ligands end with ‘ium’ and names
of neutral ligands remains as such. But exceptions are there as we use aqua for H 2O, ammine
for NH3, carbonyl for CO and nitrosyl for NO.
7. Oxidation state for the metal in cation, anion or neutral coordination compounds is
indicated by Roman numeral in parentheses.
8. The name of the complex part is written as one word.
9. If the complex ion is a cation, the metal is named same as the element.
10. The neutral complex molecule is named similar to that of the complex cation.

Some examples are

1. [Cr(NH3)3(H2O)3]Cl3
triamminetriaquachromium(III) chloride
Explanation: The complex ion is inside the square bracket, which is a cation. The amine
ligands are named before the aqua ligands according to alphabetical order. Since there are
three chloride ions in the compound, the charge on the complex ion must be +3 (since the
compound is electrically neutral). From the charge on the complex ion and the charge on the
ligands, we can calculate the oxidation number of the metal. In this example, all the ligands
are neutral molecules. Therefore, the oxidation number of chromium must be the same as
the charge of the complex ion, +3.

2. [Co(NH2CH2CH2NH2)3]2(SO4)3
tris (ethane-l,2-diamine) cobalt (III) sulphate
Explanation: The sulphate is the counter anion in this molecule. Since it takes 3 sulphates to
bond with two complex cations, the charge on each complex cation must be +3. Further,
ethane-1,2–diamine is a neutral molecule, so the oxidation number of cobalt in the complex
ion must be +3. Remember that you never have to indicate the number of cations and
anions in the name of an ionic compound.

3. [Ag(NH3)2] [Ag(CN)2]
diamminesilver (I) dicyanoargentate(I)

4. K4 [Fe(CN)6]
potassium hexacyanoferrate (II)

IUPAC names of the following coordination compounds:

1. [Pt(NH3)2Cl(NO2)]
Ans: Diamminechloridonitrito-N-platinum(II)

2. K3[Cr(C2O4)3]
Ans: Potassium trioxalatochromate(III)

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 3. [CoCl2(en)2]Cl
Ans: Dichloridobis(ethane-1,2-diamine)cobalt(III) chloride

4. [Co(NH3)5(CO3)]Cl
Ans: Pentaamminecarbonatocobalt(III) chloride

5. Hg[Co(SCN)4]
Ans: Mercury (I) tetrathiocyanatocobaltate(III)

6. [Co(NH3)6]Cl3
Ans: Hexaamminecobalt(III)chloride

7. [Co(NH3)5Cl]Cl2
Ans: Pentaamminechloridocobalt(III)chloride

8. K3[Fe(CN)6]
Ans: Potassium hexacyanidoferrate(III)

9. K3[Fe(C2O4)3]
Ans: Potassium trioxalatoferrate(III)

10. K2[PdCl4]
Ans: Potassium tetrachloridopalladate(II)

11. [Pt(NH3)2Cl(NH2CH3)]Cl
Ans: Diamminechlorido(methanamine)platinum(II) chloride

The formulas for the following coordination compounds:

1. Tetraammineaquachloridocobalt(III) chloride
Ans: [Co(NH3)4(H2O)Cl]Cl2
2. Potassium tetrahydroxidozincate(II)
Ans: K2[Zn(OH)4]

3. Potassium trioxalatoaluminate(III)
Ans: K3[Al(C2O4)3]

4. Dichloridobis(ethane-1,2-diamine)cobalt(III)
Ans: [CoCl2(en)2]+

5. Tetracarbonylnickel(0)
Ans: [Ni(CO)4]

6. Tetraamminediaquacobalt(III) chloride
Ans: [Co(NH3)4(H2O)2]Cl3

7. Potassium tetracyanidonickelate(II)
Ans: K2[Ni(CN)4]

8. Tris(ethane–1,2–diamine) chromium(III) chloride

Ans: [Cr(en)3]Cl3

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 9. Amminebromidochloridonitrito-N-platinate(II)
Ans: [Pt(NH3)BrCl(NO2)]–

10. Dichloridobis(ethane–1,2–diamine)platinum(IV) nitrate

Ans: [PtCl2(en)2](NO3)2

11. Iron(III) hexacyanidoferrate(II)

Ans: Fe4[Fe(CN)6]3

Valence Bond Theory

According to this theory, the metal atom or ion under the influence of ligands can use its
(n-1)d, ns, np or ns, np, nd orbitals for hybridisation to yield a set of equivalent orbitals of
definite geometry such as octahedral, tetrahedral, square planar and so on (Table). These
hybridised orbitals are allowed to overlap with ligand orbitals that can donate electron pairs
for bonding. This is illustrated by the following examples

Coordination Type of Distribution of hybrid

number hybridisation orbitals in space
4 sp3 Tetrahedral
4 dsp2 Square planar
5 sp3d Trigonal bipyramidal
6 sp3d2 Octahedral
6 d2sp3 Octahedral

Using valence bond theory explain geometry, hybridisation and magnetic property of [Co(NH3)6]3+.
Ans: atomic number of Co is 27.
the oxidation state of Co is +3
The electronic configuration of cobalt in +3 oxidation state is [Ar]3d64s0
Orbitals of Co+3 ion are represented as

Since NH3 is a strong filed ligand, hence pairing occurs. Two 3d, one 4s and three 4p orbitals
hybridised to yield six d2sp3 hybrid orbitals pointing towards the six corners of an octahedron

These six hybridised orbitals of Co+3 overlaps with orbitals of six NH3 ligands and six pairs of
electrons donated by six NH3 to form six coordinate bonds.

Geometry : Octahedral
Hybridisation : d2sp3
Magnetic property : Diamagnetic (no unpaired electrons)

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Using valence bond theory explain geometry, hybridisation and magnetic property of [CoF6]3+.
Ans: atomic number of Co is 27.
the oxidation state of Co is +3
The electronic configuration of cobalt in +3 oxidation state is [Ar]3d64s0
Orbitals of Co+3 ion are represented as

Since F- ion is a weak ligand filed, hence pairing does not occur. One 4s, three 4p and two outer 4d-
orbitals hybridised to yield six sp3d2 hybrid orbitals pointing towards the six corners of an octahedron

These six hybridised orbitals of Co+3 overlaps with orbitals of six F- ligands and six pairs of
electrons donated by six F- to form six coordinate bonds.

Geometry: Octahedral
Hybridisation: sp3d2
Magnetic property: paramagnetic(presence of unpaired electrons)

Using valence bond theory explain geometry, hybridisation and magnetic property of [Ni(CN)4]2-.
Ans: atomic number of Ni is 28.
the oxidation state of Ni is +2
The electronic configuration of Ni in +2 oxidation state is [Ar]3d84s0
Orbitals of Ni+2 ion are represented as

Since CN- ion is a strong field ligand, hence pairing occurs. one 3d, one 4s and two 4p -orbitals
hybridised to yield four dsp2 hybrid orbital’s pointing towards the four corners of the square planar.

These four hybridised orbitals of Ni+2 overlaps with orbitals of four CN- ligands and four pairs of
electrons donated by four CN- to form four coordinate bonds.

Geometry: square planar

Hybridisation: dsp2
Magnetic property: Diamagnetic (no unpaired electrons)

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Using valence bond theory explain geometry, hybridisation and magnetic property of [Ni(Cl)4]2-.
Ans: atomic number of Ni is 28.
the oxidation state of Ni is +2
The electronic configuration of Ni in +2 oxidation state is [Ar]3d84s0
Orbitals of Ni+2 ion are represented as

Since Cl- ion is a weak field ligand, hence don’t occurs pairing, one 4s and three 4p -orbitals hybridised
to yield four sp3 hybrid orbital’s pointing towards the four corners of the Tetrahedral geometry.

These four hybridised orbitals of Ni+2 overlaps with orbitals of four Cl- ligands and four pairs of
electrons donated by four Cl- to form four coordinate bonds.

Geometry: Tetrahedral
Hybridisation: sp3
Magnetic property: paramagnetic (presence of unpaired electrons)

Limitations of Valence Bond Theory

1. It involves a number of assumptions.
2. It does not give quantitative interpretation of magnetic data.
3. It does not explain the colour exhibited by coordination compounds.
4. It does not give a quantitative interpretation of the thermodynamic or kinetic stabilities of
coordination compounds.
5. It does not make exact predictions regarding the tetrahedral and square planar structures of
4-coordinate complexes.
6. It does not distinguish between weak and strong ligands.

Crystal Field Theory (CFT)

The crystal field theory (CFT) is an electrostatic model that describes the breaking of orbital
degeneracy in transition metal complexes due to static electric field produced by ligands.

According to crystal field theory,

 The bonding between central metal ion and a ligand is purely electrostatic (ionic).
 Ligands are treated as point charges in case of anions & dipoles in case of neutral molecules.
 The interaction between a transition metal and ligands arises from the attraction between
the positively charged metal cation and negative charge or negative pole of the ligand.
 Due to this interaction, the degeneracy of d-orbitals is lost and causes the splitting of d
orbitals.
 The splitting of five degenerate d-orbitals of metal ion into two sets of d-orbitals with
different energies under the influence of approaching ligands is called crystal field splitting.
The extent to which energies of these two sets of orbitals are split is called crystal field
splitting energy or crystal field stabilisation energy (CFSE). It denoted by ∆. This is also
measured in terms of parameter called Dq. The magnitude of splitting is arbitrarily fixed as

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