Co-ordination Complexes

Marks: 10 , Question: 2

 Introduction
 Terms used in coordination complexes
 Werner’s Theory coordination complexes
 Sidgwick’s model and Sidgwick’s effective atomic number rule
 Nomenclature of coordination compounds (Neutral type, simple
cation and complex anion and complex cation and simple anion
type)
 Valence Bond Theory of Complexes
 Application of valance bond theory in the formation of i.
Tetrahedral complexes ii. Square planar complexes and iii.
Octahedral complexes
1  Limitations of valence bond theory
 Applications of coordination complexes
 Addition or Molecular compounds
 When solutions of two or more simple stable salts are mixed together in
simple molecular proportion and the solution thus obtained is allowed to
evaporate, crystals of a new compound are obtained.
 This new compound is called addition or molecular compound.
 The formation of some addition compounds has been given below.

Simple Compounds Molecular compounds

KCl + MgCl2 + 6H2O  KCl.MgCl2.6H2O (Carnallite)

(NH4)2SO4 + FeSO4 + 6H2O  FeSO4. (NH4)2SO4. 6H2O

(Mohr’s salt)
Fe(CN)2 + 4KCN  K4[Fe(CN)6] (Potassium
ferrocyanide)
CuSO4 + 4NH3  [Cu(NH3)4]SO4

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 Types of Molecular compound
 1. Double salts
 Double salts are the addition compounds which are stable in the
solid state but give their constituent ions when dissolved in water or
in any other ionic solvents.
 In these compounds the individual properties of constituent ions are

not lost. Thus double salt retain their identity and get dissociated
into respective ions.
 Mohr’s salt, Carnallite, Potash alum etc are example of double salts.

 When crystals of carnallite, KCl.MgCl2.6H2O which is double salt are

dissolved in water the solution gives its constituent ion namely K+ ,

Mg2+& Cl- ions. Similarly aq. solution or Mohr’s salt gives the
reaction of all its constituent ions namely Fe2+, NH4+ & SO42-
ions.

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 2. Complex salt or Co-ordination compounds
 These are the addition compounds which don’t give their
constituent ions when dissolved in ionic solvents. In these
compounds the individual properties of some constituent ions
are lost.
 Complex ions don’t lose their identity in solution, These

compound retain their identity in the solid as well as solution.

 For eg :- [Cu(NH3)4]SO4 which is a complex compound
doesnot give all its constituent ion, SO42- & Cu2+ in the
solution. It gives only SO42- ion and Cu2+ ion is obtained as
[Cu(NH3)4]2+ ion which is called complex ion.

[Cu(NH3)4]SO4  [Cu(NH3)4]2+ + SO42-

 This compound gives the test of SO42- only and doesn’t show
the test of Cu2+ ion. 4
 Terms used in co-ordination complex
 Ligand
 Co-ordination no.
 Co-ordination sphere
 Charge on complex ion
 Oxidation no.

A. Ligand
• The molecular or ionic species which get attached directly to the
central metal atom or ion during the formation of complex
compound are called ligands.
• The ligands are attached to the central metal atom or ion through
co-ordination bonds therefore ligands may also be called as co-
ordinating group.
• The ligands are commonly negative ions (Such as Cl-, Br-, OH- etc.) or
neutral molecules (Such as NH3, CO, NO etc.) or may be cation
containing lone pairs of electrons for eg:- nitronium ion. In complex
ion [Co(NH3)6]3+ the six NH3 molecules which are attached with
central Co3+ ion act as ligands. 5
  To form complex compound ligands acts as a lewis base
which can donate pair of electron and central metal ion acts
as the lewis acid which accept pair of electron i.e. ligands
donate one or more electron pair to the central metal ion
forming LM co-ordinate bond.

Mn+ (Central metal ion) + xL (ligand)  [MLx]n+ (Complex compound)

 Depending on the no.of sides at which one molecule of a

ligand is co-ordinate to the central metal atom.
1. Unidentate/monodentate ligand
If ligand is attached to metal atom only by one co-ordinate bond
then the ligand is called unidentate ligand. These ligands have only
one donor atom or are co-ordinated through one electron pair.
For eg. Cl-, CN-, OH- NH3, H2O etc.
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 2. Polydentate ligand
o Ligands having two or more than two donors atoms are called polydented
ligands for e.g. Bidentate Ethylenediamine (H2NCH2CH2NH2) and oxalate ion
(-OOC-COO-).

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 Chelates
• If the ligands used more than one site for co-ordiantion with
metal to form a complex compound, such complexes are
called chelates and the ligands is known as chelating ligands
which are more stable than similar complexes containing non
chelating ligands i.e monodentate ligands.
• Chelating ligands form a chelate ring with central metal ion
this term is known as chelate effect.

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B. Coordination number (CN) of central metal atom or cation
• Coordination number (CN) of central metal atom or cation in given
complex compound is equal to the total number of donar atoms
which are actually attached with the central metal atom.
• In case of complex compounds which contain only monodentate
ligands, the coordination no. of central metal atom or cation is equal
to the number of monodentate ligands coordinated to the metal
atom. This rule doesn’t hold good for the complexes containing
polydentate ligands.
• For eg: Co-ordination no. of Co3+ ion in [Co(NH3)6]Cl3 complex is 6.
the CN of Co3+ ion in [Co(en)3]Cl3 complex is also 6 because
ethylenediamine (en) is bidentate ligand and each ligand contain
two donor atoms so total donar atom is 3 (en) molecules become
six.
• CN of the central metal atom or ion predicts the geometry of the
complex.
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 Question
i. [Ag(NH3)4]+

ii. [Fe(CN)6]3-

iii. [Fe(C2O4)3]3-

iv. [Co(en)3]Br3
v. Na[Au(CN)2]
vi. [Cr(H2O)5Cl]Cl2

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C. Co-ordination sphere and ionisable sphere
 Co-ordination sphere is the central metal ion and its
surrounding ligands this is usally written within square
bracket and behaves as a single unit. The portion outside the
square bracket is ionisable sphere.
 Eg:- [Co(NH3)6]Cl3

D. Charge on complex ion

• Charge on complex ion is the algebraic sum of charge carried
by the central metal ion and the ligands co-ordinated to it.
• For e.g in the complex ion, [Ag(CN)2]- , the Ag+ ion carries +1
charge, while two CN- carry a charge of -1 for each so the net
charge on this ion = +1+2(-1)= -1 .

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E. Oxidation number
 Oxidation number is the number with proper sign which
represents the electric charge carried by the central metal atom or
ion in the complex. Eg:- Oxidation state of Copper in [Cu(NH3)4]2+
ion is +2.

 Naming and Writing formula of a complex compound.

According to latest IUPAC system (1990) following rules are observed
while naming complex compounds.
 In naming complex salts, the name of cation is given before the
name of the anion. Eg:- [Co(NH3)5]Cl3 Pentaammine cobalt
(III) chloride, K4[Fe(CN)6] Potassium hexacyanoferrate (II)

 In complex ion or molecule, the ligands are named before the

metal. More than one type of ligands are in such ion or molecule
which are listed in alphabetical order. 12
 Anionic ligands end in the letter ‘o’, whereas neutral one is same but special
name are given to water and ammonia.

 If the complex is anion, its name ends in –ate. For example, [Fe(CN)6]4-
hexacyanoferrate (II) ion.
 The oxidation number of the central metal atom is written in Roman
numerals. For eg:- [Co(NH3)5 Cl]2+, where cobalt has +3 oxidation number and
the IUPAC of that complex is written as Pentaammine chloro cobalt (III) ion.
 If in a complex ion, there are more than one each kind of ligands, a greek
prefix (i.e. di, tri, tetra, penta and hexa) is used to determine the number of
same ligand. For example [Co(NH3)5Br]2+ Pentaammine bromo cobalt (II) ion,
where penta indicates there are 5 ammine groups.
 If the ligand itself contains such type of greek prefix like
ethylenediammine, dimethyglyoximato, the ligand is denoted by
alternative prefixes like bis, tris, tetrakis, pentakis and hexakis are used.
Eg. Tris ethyldiammine cobalt (III) chloride [Co(en)3]Cl3 . 13
 While naming a complex acid of transition metals, ending –ic is
used. Eg:- H4[Pt(CN)6] is named as hexacyanoplatinic (II) acid.
 For naming bridging ligands, there is used before the bridging
ligand. [(NH3)5-Cr-OH-Cr-(NH3)5]Cl5 µ -hydroxo bis-
{pentaamminechromium(III)} chloride.

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 Effective Atomic Number (EAN) rule
 According to professer N.V. Sidgwick postulated that, “the total no.
of ligands attached to the central metal atom makes the total no. of
electrons around the central metal atom identical to that of nearest
nobel gas.”
 From above postulate, the ligands have donated a certain no. of
electrons to the central metal ion, including those gained from the
ligands in bonding is called effective atomic number(EAN) of the
central metal ion.
 When the EAN is 36(Kr), 54(Xe), 86(Rn)the rules is said to be
followed and hence complex is stable.
 EAN of a central metal atom or ion in a given complex is given by the
following formula.
 EAN = (Z-X) + n.y
 where Z = atomic no. of central metal atom, X = O.S. of metal, n =
no. of ligands, y = no. of electron donated by one ligand.
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 Example [Fe(CN)6]4-
EAN = (z-x) + n.y
= (26-2) + 6.2
= 24 + 12 = 36 ~ (Kr)

Find out EAN of following.

i. Cr(CO)6
ii. Fe(CO)5
iii. [Co(NH3)6]3+
iv. [PtCl6]2-
v. [Cd(NH3)4]2+
vi. [Ag(NH3)4]+
vii. K3[Fe(CN)6]

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 Werner’s theory of coordination compounds
In 1893, Alfred Werner put forward a theory, called Werner’s theory of
coordination compounds to explain the structure and nature of bonding in
coordination compounds.
According to it.
1. In coordination compounds, the metals possess two types of valencies:
a. Primary valencies/ Principle valencies
 The primary valency of the central metal atom in a complex compound
corresponds to the oxidation state (or O.N) of that metal. It is referred as
ionizable valency.
 The primary valencies are the no. of charges on the complex ion and
non-directional. So the species satisfying primary valency don’t give aany
geometry to the complex compound.
 They are indicated by dotted lines.
b. Secondary valencies
• Secondary valencies are non ionisable valencies.
• The no. of Secondary valencies are equal to the no. of ligand atoms
coordinated to the central metal atom.

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• It is also called coordination number of central metal atom.
• These are directional and give definite geometry to the complex.
• Which are shown by thick lines.
Example
Aq. Solution of [Co(NH3)6]Cl3 undergoes ionisation to give 3Cl- ions which
satisfy primary valency of Co-atom and are obtained in free state. Thus primary
valency is 3.
[Co(NH3)6]Cl3 [Co(NH3)6]3+ + 3Cl-
In [Co(NH3)6]Cl3 , Secondary valency of Co-atom is six because it is satisfied by
six NH3 molecules i.e. coordination number of Co atom in this complex is six.

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2. Secondary Valencies are directed towards fixed position in space.
 Secondary valencies have directional nature.
 Hence the no. of species satisfing the coordination number gives definite
geometry to the complex ion. Eg. The complex ion [Co(NH3)6]3+ is octahedral.
 When the coordination number of the central metal atom in complex
compound is 2, 3, 4 or 6 the geometry of the complex compound would be
linear, trigonal planner, trtrahedral or square planner or octahedral
respectively.

Werner’s observations/ Evidences

I. The central metal atom or ligands don’t retain any individual properties in
the complex compounds. For eg:- [Co(NH3)6]Cl3 solution doesn’t give any
reaction either of Co3+ ions or NH3. However, it gives reaction of Cl- ions.
II. Mixed complexes can also be formed, in which some ligands are neutral
while the others are anion. Eg:- [Co(NH3)6]Cl3, [Co(NH3)5Cl]Cl2
[Co(NH3)4Cl2]Cl & [Co(NH3)3Cl3] . Here second and third complexs are mixed
complex. 19
 Describe the simple test to distinguish between the
following pairs of compounds on the basis of Werner’s
theory. [Co(NH3)5Cl]SO4 and [Co(NH3)5SO4]Cl

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 Valance Bond Theory (VBT)
This theory was proposed by Linus Pauling who was awarded by the Nobel
prize in Chemistry in 1954. VBT mainly explain nature of bonding, geometry
and magnetic properties of the coordination compound.
Basic Postulates
1. The central metal atom in coordination compound provide the no. of
vacant orbital equal to its coordination no. for the formation of coordinate
bond with ligand.
2. In the presence of strong ligand (such as CO, CN- etc.) the pairing of
electron takes place in the inner (n-1)d atomic orbital of transitional
element or central metal atom whereas in the presence of weak ligand
(such as Cl-, OH-. H2O etc.) no such a pairing of electron takes place.
3. The available vacant orbital undergo hybridization to produce equal and
identical new hybrid orbital. The geometry of the molecule is determined
on the basis of nature of hybrid orbital. i.e. sp3, dsp2 and d2sp3 (orsp3d2)
hybridization results in the formation of complex of geometry tetrahedral,
square planner and octahedral respectively.
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4. Ligands are in the form of group which donate no. of unpaired electron to
the hybridized orbital of the central metal atom where ligands are electron
pair donor (lewis base) and central metal atom is an electron pair acceptor
(lewis acid).
5. The presence of unpaired electron in the complex configuration makes the
complex paramagnetic whereas the presence of only paired electron makes
the complex diamagnetic.

Drawback : It explains the bonding in complexes only qualitatively, but

cannot explain the detailed magnetic properties as well as absorption spectra
of these compounds.

Note: weak field ligands (I-, Cl-, N3-, HO-, H2O etc.)
strong field ligands (CO, CN-, en, NO2, PPh3, NCS-, py etc.)
NH3 is weak ligand except when it is bonded with Co.

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Table: Geometry of some complexes

Types of Geometrical Examples

hybridizati shape
on

(a) sp3 Tetrahedral [NiCl4]2-, [FeCl4]2-, [FeCl4]-,

[Cu(CN)4]2-, [Ni(CO)4],
[Zn(NH3)4]2+, [Cd(NH3)4]2+ etc.

(a) dsp2 Square planar [Ni(CN)4]2-, [Cu(NH3)4]2+,

[Co(CN)4]2- etc.

(a) d2sp3 or Octahedral [Cr(NH3)6]2+, [FeF6]4-,

sp3d2 [Fe(CN)6]3-, [Co(NH3)6]3+,
[Co(CN)6]3-, [CoF6]3- etc.

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Explanation of formation of some complexes
I. Octahedral Complexes (CN = 6)
II. Tetrahedral Complexes (CN = 4)
III. Square planar Complexes (CN = 4)

Octahedral complexes
These complexes are formed by d2sp3 (inner orbital) or sp3d2 (outer
orbital) hybridization. The resulting complex has octahedral geometry.
3d+3d + 4s + 4p+4p+4p  d2sp3 (inner orbital)
4s + 4p+4p+4p + 4d+4d  sp3d2 (outer orbital)

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Octahedral structure of complex
where, M = central metal atom
L = ligand

Note: outer orbital complexweak ligandsno pairing of

electronsparamagnetic except d10 configurationsp3d2called high
spin complex or spin free complex.
Inner orbital complexstrong ligandpairing of electronsusually
diamagnetic or weakly paramagneticd2sp3low spin complex or
spin pair complex.
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Example
Bonding in [Ni(NH3)6]2+ : In the complex ion, the central metal is in +2
oxidation state, so it (Ni atom) loses two electrons. Here the
coordination number of Ni atom is six, therefore, the central Ni-atom
makes available six vacant orbitals for hybridization. Now we can write
the bonding scheme as follows:
Outer orbitals in Ni2+ ion
3d 4s 4p 4d
↑↓ ↑↓ ↑↓ ↑ ↑

Here NH3 is weak ligand. Empty sp3d2 hybridized orbitals of Ni2+

Sp3d2 vacant orbital 4d
3d
↑↓ ↑↓ ↑↓ ↑ ↑

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sp3d2 hybridized orbitals
3d Sp3d2 hybridization 4d
↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓

Six pairs of electrons

from six NH3 ligands
(octahedral geometry)

 The complex is thus

octahedral, because Ni-atom
is in the state of sp3d2
hybridization which contains 2
unpaired electrons and is
paramagnetic.
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Bonding in [Cr(NH3)6]3+ : In the complex ion, the central metal is in +3
oxidation state, so it (Cr atom) loses three electrons. Here the
coordination number of Cr atom is six, therefore, the central Cr-atom
makes available six vacant orbitals for hybridization. Now we can write
the bonding scheme as follows:
Outer orbitals in Cr3+ ion
4p
3d 4s
↑ ↑ ↑

Empty d2sp3 hybridized orbitals of Cr3+

3d d2sp3 vacant hybrid orbitals
↑ ↑ ↑

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d2sp3 hybridized orbitals
3d d2sp3 hybrid orbitals

↑ ↑ ↑ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓

Six pairs of electrons from

six NH3 ligands.
(octahedral geometry)
(inner orbital complex)

 The complex is thus

octahedral which
contains three unpaired
electrons and
paramagnetic.

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S.N. Complex Hybridizat No. of Magnetic
ion unpaire properties
d es

1 [Ni(NH3)6]2+ sp3d2 2 paramagnetic

2 [FeF6]4- sp3d2 4 Paramagnetic
3 [Fe(CN)6]3-
4 [Fe(CN)6]4-
5 [Co(CN)6]3-
6 [CoF6]3-
7 [Co(NH3)6]3+ d2sp3 0 diamagnetic
8 [Cr(NH3)6]3+ d2sp3 3 paramagnetic
9 [Cu(NH3)6]+

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Tetrahedral Complex
Those complexes are formed by sp3 hybridization and resulting
complex has tetrahedral geometry.

Weak ligandtetrahedral complex

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Example
Bonding in [MnCl4]2- : In the complex ion, the central metal is in +2
oxidation state, so it (Mn atom) loses two electrons. Here the
coordination number of Mn atom is four, therefore, the central Mn-
atom makes available four vacant orbitals for hybridization. Now we
can write the bonding scheme as follows:
Outer orbitals in Mn2+ ion
3d 4s 4p
↑ ↑ ↑ ↑ ↑

The Cl- is a weak ligand. So, it doesn’t force two unpaired d-electrons to
pair up. Therefore they remain unpaired in the 3d-orbitals. Hence, the
Mn atom makes available one 4s and three 4p orbitals for sp3
hybridization.

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Hybridized sp3 orbitals in [MnCl4]2-
3d sp3 hybrid orbital
↑↓ ↑↓ ↑↓ ↑↓

Four pairs of
electrons from four
Cl- ligands.
(tetrahedral
complex)
There are presence of unpaired electrons therefore it is paramagnetic.

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Bonding in [Ni(CO)4]0
Outer electronic configuration of nickel (in its zero oxidation state) is
3d8, 4s2 or 3d10. Four electron pairs one from each CO molecules,
occupy the empty one 4s and three 4p orbitals and they hybridize to
form four sp3 hybrid orbital of tetrahedral geometry. Since the
compound [Ni(CO)4] contains no unpaired electron so it is
diamagnetic.
Atomic orbitals in Ni
3d 4s 4p
↑↓ ↑↓ ↑↓ ↑ ↑ ↑↓

Vacant hybrid sp3 orbitals in Ni.

3d
Sp3 vacant
↑↓ ↑↓ ↑↓ ↑↓ ↑↓ hybrid orbital

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Hybridized sp3 orbitals in [Ni(CO)4]0

↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓

Tetrahedral geometry

Note: CO is strong ligand. So the two unpaired electrons in Ni are

paired up against Hund’s rule. The two 4s electrons move to the 3d
orbitals and thus Ni-atom makes available 4s orbital for sp3 hybridized.

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Square planner complex
These complexes are formed by dsp2 hybridization as a resulting
complex of square planar geometry. These complexes are usually
formed by strong ligand.
d+s+p+p  dsp2

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Bonding in [Ni(CN)4]2-
O.S. of Nickel = +2
Outermost orbital in Ni2+
3d 4s 4p
↑↓ ↑↓ ↑↓ ↑ ↑

CN- is strong ligand and it follows against Hund’s rule. So it forces two
unpaired d- electrons to pair up.
Vacant dsp2 orbital
3d dsp2 vacant orbital 4p
↑↓ ↑↓ ↑↓ ↑↓

Hybridized dsp2 orbitals in [Ni(CN)4]2-

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 3d 4p

dsp2 hybrid orbitals,

Four pairs of electrons
from four CN- ligands.
(Square planar geometry)

It contains no unpaired electron, so it is diamagnetic.

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 S.N. Complexes dn hybridiz Unpai Magnetic
ation red es propertie
s
1 [Ni(CN)4]2- d8 dsp2 0 Diamagnet
ic

2 [Co(CN)4]2- d7 dsp2 1 paramagn

etic

3 [Cu(NH3)4]2+ d9 dsp2 1 paramagn

etic

Application of Coordination compounds.

[A] In analytical chemistry
[B] In the field of medicine
[C] In nature

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Questions
1. Differentiate between inner and outer orbital complexes. Explain
the formation of [Ni(CO)4]0 complex on the basis of VBT. Also
predict its geometry and magnetism with reason.
2. Compare the magnetic behavior of the complex entities
[Fe(CN)6]4- and [FeF6]3- using valence bond theory.

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