COORDINATION COMPOUNDS; THEIR

NOMENCLATURE AND ISOMERISM 1

| TOPIC 1 |
WERNER’S THEORY OF COORDINATION COMPOUNDS
The coordination compounds play a vital role in metallurgy and
medicine. They are a vital component of every walk of life. Examples
include substances like vitamin B12, haemoglobin, and chlorophyll, dyes
and pigments, and catalysts used in preparing organic substances.
Although, the chemical composition of such compounds was readily
established by existing analytical methods, their chemical nature was
puzzling and highly controversial.
Werner’s theory (1898) explains the structure of coordination
compounds. When silver nitrate was added to CoCl3·6NH3, all three
chlorides were converted to silver chloride. However, when silver nitrate
was added to CoCl3·5NH3, only 2 of the 3 chlorides formed silver
chloride. When CoCl3·4NH3 was treated with silver nitrate, one of the
three chlorides precipitated as silver chloride.
Postulates of Werner’s Theory
(1) The central metal atom in the coordination compound exhibits
two types of valency namely, primary and secondary linkages or
valences.
(2) Primary valences are ionizable valences, satisfied by anions and
determines the charge on the complex ions.
(3) Secondary valences are non-ionisable valences (ligands), satisfied
by ligands and determines the coordination number of the metal
atom.
(4) Based on the Werner theory, the complex CoCl3·6NH3 of [Co(NH3)6]
Cl3, i.e., hexaamminceobalt(III) chloride can be shown as;
NH33
NH Cl
HH33NN NH3 Primary
Primaryvalencies
valencies
Secondary
Secondaryvalencies
valencies
ClCl Co
Co

HH33NN NH3
NH3
NH3 Cl
Cl
NH3

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 The geometry of the complex is determined by the number and
arrangement of the ligands in space around the central metal atom
(or ion).
Limitations of Werner’s Theory
(1) This theory could not explain the inability of all elements to form
coordination compounds.
(2) The Werners theory could not explain the directional properties of
bonds in various coordination compounds.
(3) It could not explain the colour, the magnetic and optical properties
shown by coordination compounds.
(4) It does not explain the stability of coordination complexes.
Difference between Coordination Compounds and Double Salts
Addition compounds which do not dissociate into simple ions when
dissolved in water and retain their properties in solution are coordination
compounds.
For example- Potassium ferrocyanide K4 [Fe(CN)6 ] gets dissociated as
4K+ + [Fe (CN)6]-. Addition compounds which dissociate into simple ions
when dissolved in water are double salts. For Example: Mohr's salt
+
FeSO4·(NH4)2SO4·6H2O get dissociated into Fe2+, NH4 and SO42- ions.

Table: Differences between double salt and a coordination complex

S. No. Double Salt Coordination Compound

(1) Double salts lose their identity They don't lose their identity
in aqueous solution by in aqueous solution as they
completely dissociating into do not ionize completely (the
ions in the solvent. complex ion further does not
get ionized).
(2) They give test for all the They do not show test for all
constituent ions. their constituent ions Example:
Example: K4[Fe(CN)6], in K4[Fe(CN)6], it
K2SO4.Al2(SO4)3.24H2O does not show the test for Fe2+
and CN–

Coordination Compounds 3
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Example 1.1: FeSO4 solution mixed with (NH4)2SO4 solution in 1 : 1
molar ratio gives the test of Fe2+ ion but CuSO4 solution mixed with
aqueous ammonia in 1 : 4 molar ratio does not give the test of Cu2+
ion. Explain why? [NCERT]
Ans. When FeSO4 and (NH4)2SO4 solutions are mixed in 1 : 1 molar ratio,
a double salt known as Mohr’s salt is formed. It has the formula
FeSO4.(NH4)2SO4.6H2O. In aqueous solution, the salt dissociates as :
FeSO4 .(NH4 )2 SO4 .6H2O( aq )
2+ + 2-
Fe ( aq ) + 2NH4( aq ) + 2SO4 ( aq ) + 6H2O

The
solution gives the tests for all the ions including Fe2+ ions. On
the other hand, when CuSO4 and NH3 are mixed in the molar ratio
of 1 : 4 in solution, a complex [Cu(NH3)4]SO4 is formed. Since, the
Cu2+ ions are a part of the complex entity (enclosed in square
bracket), it will not give their characteristic tests as given by Fe2+
ions.
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4 Chemistry Class XII

 OBJECTIVE Type Questions

Multiple Choice Questions

[ 1 mark each ]

1. The compound [Co(NH3)5Cl]SO4 is isomeric with the compound

[Co(NH3)5SO4]Cl. Which of the following rows correctly
represents the oxidation state of cobalt in these compounds?

Rows [Co(NH3)5CI]SO4 [Co(NH3)5SO4]CI

A +2 +3
B +3 +2
C +2 +1
D +3 +3

(a) A (b) B
(c) C (d) D [CBSE Question Bank 2023]
Ans. (d) D
Explanation: Oxidation state of cobalt is +3 in both the given
compounds, i.e., in [Co(NH3)5Cl]SO4 and [Co(NH3)5SO4]Cl.

VERY SHORT ANSWER Type Questions (VSA)

[ 1 mark each ]

2. What do you undersatand by 'denticity of a ligand'?

[CBSE 2011]
Ans. The number of coordinating groups present in a ligand is called
the denticity of the ligand. For example: EDTA can bind through
two nitrogen and four oxygen atoms to a central metal ion and
thus is regarded as the hexadentate ligand.

Coordination Compounds 5
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 SHORT ANSWER Type-I Questions (SA-I)
[ 2 marks each ]

3. Using IUPAC norms write the formulae for the following:

(A) Sodium dicyanidoaurate (I)
(B) Tetraamminechloridonitrito-N-platinum (IV) sulphate
[CBSE 2017]
Ans. (A) Na[Au(CN2)]
Sodium dicyanidoaurate (I)
(B) [Pt(NH3)4(Cl)(NO2)]SO4
Tetraamminechloridonitrito-N-platinum (IV) sulphate.

SHORT ANSWER Type-II Questions (SA-II)

[ 2 marks each ]

4. Explain the following giving examples:

(A) Ambidentate ligand
(B) Coordination number
(C) Chelate complex [Delhi Gov. SQP Term-2 2022]
Ans. (A) L igand which can ligate through two different atoms is called
ambidentate ligand. Examples of such ligands are the NO2–
and SCN– ions. NO2– ion can coordinate either through nitrogen
or through oxygen to a central metal atom/ion.
(B) The coordination number of a metal ion in a complex can be
defined as the number of ligand donor atoms to which the
metal is directly bonded. For example, in the complex ion,
[Ni(CN)4]2– coordination number of Ni is 4.
(C) 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. Such complexes are called chelate complexes. E.g.,
[Co(en)3]3+. [Delhi Gov. Marking Scheme SQP Term-2 2022]

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Coordination Compounds 7
 BONDING IN COORDINATION
2
COMPOUNDS

| TOPIC 1 |
VALENCE BOND THEORY (VBT)

Postulates
(1) The Valence Bond Theory, proposed by Linus Pauling, satisfactorily
explains the structure and magnetic properties of a large number of
coordination compounds.
(2) According to this theory, the metal atom or ion under the influence
of ligands can use its (n-1)d, ns, np, nd orbitals for hybridisation. This
would lead to yield a set of equivalent orbitals of definite geometry
called Hybridised orbitals .
(3) These include octahedral, tetrahedral, square planar and other such
geometrical arrangements. A ligand orbital containing a lone pair of
electrons forms a coordinate covalent bond by overlapping with the
hybridised orbitals of the metal ion.

Table: Number of Orbitals and Type of Hybridisations

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
(4) The central metal atom (or) ion has the required number of vacant
orbitals for accommodating the electrons donated by the ligands.
The number of vacant orbitals is equal to the coordination number
of the metal ion for a particular complex.

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 3d 4s 4p 4d
Orbitals of
Co3+ ion
Vacant orbitals
Coordination number of M(Co 3+)=4

Pictorial representation of VBT

Octahedral Complexes
There are two types of hybridisations involved in octahedral complexes:
d2sp3 and sp3d2
In the formation of a octahedral complex, if the metal utilises its inner
d-orbitals, then such a complex is called an inner orbital complex (or)
low-spin (or) spin-paired complex. If the metal utilises its outer d-orbitals,
then such a complex is called an outer orbital complex (or) high-spin (or)
spin-free complex.
Inner d-orbital Outer d-orbital
Orbitals 3d 4s 4p 4d
of
Metal Inner orbital Outer orbital
complex complex
( Low- spin or ( High- spin or
spin-paired complex) spin-free complex)

Octahedral Complexes with d2sp3 hybridization

Hybridisation of [Co(NH3)6]3+
In this complex Co3+ metal ion has seven electrons in its 3d orbital. In its
ground state configuration, it has four unpaired electrons in 3d orbital,
while 4s, 4p orbitals are empty.
27Co =1s2,2s22p6,3s23p63d7,4s2
3+
Co = 1s2,2s22p6,3s23p63d6
3d 4s 4p

3d 4s 4p
× × × × × ×

d 2sp3-hybridisation

Coordination Compounds 9
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 NH3 NH3
H3N NH3 H3N NH3
3+
Co Co
H3N NH3 H3N NH3
NH3 NH

Structure of [Co(NH3)6]3+ is octahedral

(1) Each amine ligand donates 6 pairs of electrons. (12 electrons).
(2) Geometry of complex: Octahedral structure due to d2sp3
hybridisation (inner orbital complex or low spin complex, all electrons
are paired).
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10 Chemistry Class XII

 OBJECTIVE Type Questions

Multiple Choice Questions

[ 1 mark each ]

1. The CFSE for octahedral [CoCl6]4– is 18,000 cm–1. The CFSE for
tetrahedral [CoCl4]2– will be:
(a) 18,000 cm–1 (b) 16,000 cm–1
(c) 8,000 cm–1 (d) 20,000 cm–1
[CBSE SQP 2022]
Ans. (c) 8,000 cm–1 [CBSE Marking Scheme SQP 2022]
Explanation: The CFSE for tetrahedral complex is given by:
4 4
Dt = ∆o × 18000 = 8000 cm–1
9 = 9

SHORT ANSWER Type-I Questions (SA-I)

[ 2 marks each ]

4. Magnetic moment of [MnCl4]2– is 5.92 BM. Explain giving

reason. [NCERT Exemplar]
Ans. The magnetic moment is calculated by the formula given below:

m = n( n + 2)

n( n + 2) = 5.92
2
n(n + 2)= (5.92) = 35.0464 ~ 35
n2 + 2n – 35 =0
On solving, the value of n is equal to 5, i.e., the number of unpaired
electrons is 5. In this complex, Mn2+ ion has [Ar]3d5 configuration.
The hybridisation of this complex will be sp3, and its structure is
tetrahedral.

SHORT ANSWER Type-II Questions (SA-II)

[ 3 marks each ]
4. Answer the following questions:
(A) [Ni(H2O)6]2+(aq) is green in colour whereas [Ni(H2O)4 (en)]2+
(aq) is blue in colour, give reason in support of your answer.

Coordination Compounds 11
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 (B) Write the formula and hybridization of the following
compound:
tris(ethane-1,2–diamine) cobalt(III) sulphate
 [CBSE SQP Term-2 2022]
Ans. (A) The colour of coordination compound depends upon the type
of ligand and d-d transition taking place.
H2O is weak field ligand, which causes small splitting, leading
to the d-d transition corresponding green colour, however
due to the presence of (en) which is strong field ligand , the
splitting is increased. Due to the change in t2g - eg splitting the
colouration of the compound changes from green to blue.
[CBSE Marking Scheme SQP Term-2 2022]
Related Theory
The cause of the colour of coordination compounds can be explained by

Crystal Field Theory. The colours exhibited by transition-metal complexes are
caused by:
(1) Excitation of an electron from a lower-energy d orbital to a higher-energy
d orbital, which is called a d–d transition.
(2) The specific ligands(strong or weak) coordinated to the central metal atom.

(B) Formula of the compound is [Co(H2NCH2CH2NH2)3]2 (SO4)3

The hybridisation of the compound is: d2sp3.
[CBSE Marking Scheme SQP Term-2 2022]

Related Theory
 According to Valence Bond Theory (VBT), [Co(en)3]2(SO4)3 forms inner orbital
complex involving d2sp3 hybridisation.
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12 Chemistry Class XII

 TOPPER’S CORNER

SHORT ANSWER Type-II Questions (SA-II)

[ 3 marks each ]
1. (A) Write the IUPAC name of the following complex:
[Co(NH3)4(H2O)Cl]Cl2
(B) What is the difference between an Ambidentate ligand and
a Bidentate ligand?
(C) Out of [Fe(NH3)6]3+ and [Fe(C2O4)3]3–, which complex is
more stable and why?
Ans.

[CBSE Topper 2022]

Coordination Compounds 13
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