Coordination compounds and double salts:

 When two or more stable compounds in solution are mixed

together and allowed to evaporate, in certain cases there is a
possibility for the formation of double salts or coordination
compounds.
 For example when an equimolar solution of ferrous sulphate
and ammonium sulphate are mixed and allowed to crystallise, a

double salt namely Mohr's salt (Ferrous ammonium sulphate,

FeSO4.(NH4)2SO4.6H2O is formed.
 Let us recall the blood red colour formation in the inorganic qualitative
analysis of ferric ion, the reaction between ferric chloride and potassium
thiocyanate solution gives a blood red coloured coordination compound,
potassium ferrithiocyanate K3[Fe(SCN)6].
 If we perform a qualitative analysis to identify the constituent ions present in
both the compounds, Mohr's salt answers the presence of Fe2+ ,NH4+ and SO2- 4

ions, whereas the potassium ferrithiocyanate will not answer Fe3+ and SCN-
ions.
 From this we can infer that the double salts lose their identity and dissociates
into their constituent simple ions in solutions , whereas the complex ion in
Werner's theory of coordination
 Swiss chemist Alfred Werner was the first one to propose a theory
compounds:
of coordination compounds to explain the observed behaviour of
them.

 Let us consider the different coloured complexes of cobalt(III)

chloride with ammonia which exhibit different properties as
shown below.

 In this case, the valences of the elements present in both the reacting molecules,
cobalt(III) chloride and ammonia are completely satisfied. Yet these substances
react to form the abovementioned complexes.
To explain this behaviour Werner postulated his theory as
follows
1. Most of the elements exhibit, two types of valence namely primary valence and
secondary valence and each element tend to satisfy both the valences. In modern
terminology, the primary valence is referred as the oxidation state of the metal atom
and the secondary valence as the coordination number. For example, according to
Werner, the primary and secondary valences of cobalt are 3 and 6 respectively.

2. The primary valence of a metal ion is positive in most of the cases and zero in
certain cases. They are always satisfied by negative ions.
For example in the complex CoCl3.6NH3,The primary valence of Co is +3 and is
satisfied by 3Cl- ions.

3. The secondary valence is satisfied by negative ions, neutral molecules, positive

ions or the combination of these.
For example, in CoCl3.6NH3 the secondary valence of cobalt is 6 and is satisfied by six
neutral ammonia molecules, whereas in CoCl3.5NH3 the secondary valence of cobalt
is satisfied by five neutral ammonia molecules and a Cl- ion.
4. According to Werner, there are two spheres of attraction around a metal
atom/ion in a complex.
The inner sphere is known as coordination sphere and the groups present in this
sphere are firmly attached to the metal.
The outer sphere is called ionisation sphere.
The groups present in this sphere are loosely bound to the central metal ion and
hence can be separated into ions upon dissolving the complex in a suitable solvent.
CoCl3.6NH3
5.The primary valences are non-directional while the secondary valences are
directional. The geometry of the complex is determined by the spacial
arrangement of the groups which satisfy the secondary valence.
For example, if a metal ion has a secondary valence of six, it has an octahedral
geometry. If the secondary valence is 4, it has either tetrahedral or square planar
geometry.
The following table illustrates the Werner's postulates.

Limitations of Werner’s theory:

Even though, Werner’s theory was able to explain a number of properties of coordination
compounds, it does not explain their colour and the magnetic properties.
Definition of important terms pertaining to co-ordination compounds:

Coordination entity:
Coordination entity is an ion or a neutral molecule, composed of a central
atom, usually a metal and the array of other atoms or groups of atoms
(ligands) that are attached to it. In the formula, the coordination entity is
enclosed in square brackets.
For example, in potassium ferrocyanide, K4[Fe(CN)6], the
coordination entity is [Fe(CN)6]4- .
In nickel tetracarbonyl, the coordination entity is [Ni(CO)4].
Central atom/ion:
The central atom/ion is the one that occupies the central position in a
coordination entity and binds other atoms or groups of atoms (ligands) to
itself, through a coordinate covalent bond.
For example, in K4[Fe(CN)6], the central metal ion is Fe2+ . In the
coordination entity [Fe(CN)6]4- the Fe2+ accepts an electron pair from
each ligand, CN- and thereby forming six coordinate covalent bonds with
them.
since, the central metal ion has an ability to accept electron pairs, it is
referred to as a Lewis acid.
Ligands:
The ligands are the atoms or groups of atoms bound to the central
atom/ion. The atom in a ligand that is bound directly to the central metal
atom is known as a donor atom.
For example, in K4[Fe(CN)6], the ligand is CN- ion, but the donor
atom is carbon and in [Co(NH3)6]Cl3 the ligand is NH3 molecule and
the donor atom is nitrogen.
Coordination sphere:
The complex ion of the coordination compound containing the
central metal atom/ion and the ligands attached to it, is collectively
called coordination sphere and are usually enclosed in square
brackets with the net charge. The other ionisable ions, are written
outside the bracket are called counter ions.
For example, the coordination compound K4[Fe(CN)6] contains the
complex ion [Fe(CN)6] and is referred as the coordination sphere.
4-

The other associated ion K+ is called the counter ion.

Coordination polyhedron:
The three dimensional spacial arrangement of ligand atoms/ions that
are directly attached to the central atom is known as the
coordination polyhedron (or polygon).
For example,
in K4[Fe(CN)6], the coordination polyhedra is octrahedral.
The coordination polyhedra of [Ni(CO)4] is tetrahedral.
Coordination number:
The number of ligand donor atoms bonded to a central
metal ion in a complex is called the coordination number
of the metal. In other words, the coordination number is
equal to the number of σ-bonds between ligands and the
central atom.
For example,
i. In K [Fe(CN) ], the coordination number of Fe2+ is 6.
4 6

ii. In [Ni(en) ]Cl , the coordination number of Ni2+ is also 6.

3 2

Here the ligand 'en' represents ethane-1,2-diamine

(NH -CH -CH -NH ) and it contains two donor atoms
2 2 2 2

(Nitrogen)
Each ligand forms two coordination bonds with nickel.
So,totally there are six coordinationnbonds between them.
Oxidation state (number):
The oxidation state of a central atom in a coordination
entity is defined as the charge it would bear if all the
ligands were removed along with the electron pairs that
were shared with the central atom.
In naming a complex, it is represented by a Roman
numeral.

For example,
in the coordination entity [Fe(CN)6]4- the oxidation state of
iron is represented as (II).
The net charge on the complex ion is equal to the sum of the
oxidation state of the central metal and the charge the on the ligands
attached to it.

Using this relation the oxidation number can be calculated as follows

Types of complexes:
The coordination compounds can be classified into the following types
based on
(i) The net charge of the complex ion

(ii) kinds of ligands present in the coordination entity.

Classification based on the net charge on the complex:

A coordination compound in which the complex ion
I. carries a net positive charge is called a cationic complex.
Examples: [Ag(NH3)2]+, [Co(NH3)6]3+ , [Fe(H2O)6]2+, etc
ii. carries a net negative charge is called an anionic complex.
Examples: [Ag(CN)2]-, [Co(CN)6]3- , [Fe(CN)6]4-, etc
iii. bears no net charge, is called a neutral complex.
Examples: [Ni(CO)4], [Fe(CO)5] , [Co(NH3)3(Cl)3], etc
Classification based on kind of ligands:
A coordination compound in which
i. the central metal ion/atom is coordinated to only one kind of
ligands is called a homoleptic complex.
Examples: [Co(NH3)6]3+ , [Fe(H2O)6]2+ ,

ii. the central metal ion/atom is coordinated to more than one kind
of ligands is called a heteroleptic complex.

Example, [Co(NH3)5Cl]2+ , [Pt(NH3)2Cl2)]

Nomenclature of coordination compounds
• In the earlier days, the compounds were named after their
discoverers.
For example,
• K[PtCl3(C2H4)] was called Zeise’s salt

• [Pt(NH3)4][PtCl4] is called Magnus’s green salt etc...

• There are numerous coordination compounds that have been
synthesised and characterised.
• The International Union of Pure and Applied Chemistry (IUPAC) has
developed an elaborate system of nomenclature to name them
systematically.
The guidelines for naming coordination compounds based
on IUPAC recommendations (2005) are as follows:
Naming of coordination compounds using IUPAC guidelines.
More examples with names are given in the list below for better
understanding of IUPAC Nomenclature:
HOME WORK
Isomerism in coordination compounds
 Isomerism is the phenomenon in which more than one
coordination compounds having the same molecular formula have
different physical and chemical properties due to different
arrangement of ligands around the central metal atom.
 The following flow chart gives an overview of the common types
of isomerism observed in coordination compounds,
Structural isomers
 The coordination compounds with same formula, but have
different connections among their constituent atoms are called
structural isomers or constitutional isomers.
Linkage isomers:
 This type of isomers arises when an ambidentate ligand is bonded
to the central metal atom/ion through either of its two different
donor atoms.
 In the below mentioned examples, the nitrite ion is bound to the
central metal ion Co3+ through a nitrogen atom in one complex,
and
through oxygen atom in other complex.
[Co(NH3)5(NO2)]2+
Coordination isomers:
 This type of isomers arises in the coordination compounds having
both the cation and anion as complex ions. The interchange of one
or more ligands between the cationic and the anionic coordination
entities result in different isomers.
 For example, in the coordination compound, [Co(NH3)6][Cr(CN)6]
the ligands ammonia and cyanide were bound respectively to
cobalt and chromium while in its coordination isomer
[Cr(NH3)6][Co(CN)6] they are reversed.
Ionisation isomers:
 This type of isomers arises when an ionisable counter ion (simple
ion) itself can act as a ligand. The exchange of such counter ions
with one or more ligands in the coordination entity will result in
ionisation isomers. These isomers will give different ions in
solution.
 For example, consider the coordination compound [Pt(en)2Cl2]Br2.
In this compound, both Br- and Cl- have the ability to act as a
ligand and the exchange of these two ions result in a different
isomer [Pt(en)2Br2]Cl2. In solution the first compound gives Br-
ions while the later gives Cl- ions and hence these compounds are
called ionisation isomers.
Solvate isomers.
 The exchange of free solvent molecules such as water , ammonia,
alcohol etc.. in the crystal lattice with a ligand in the coordination
entity will give different isomers. These type of isomers are called
solvate isomers.
 If the solvent molecule is water, then these isomers are called
hydrate isomers.
 For example, the complex with chemical formula CrCl3.6H2O has
three hydrate isomers as shown below.
Stereoisomers:
 Similar to organic compounds, coordination compounds also
exhibit stereoisomerism.
 The stereoisomers of a coordination compound have the
same chemical formula and connectivity between the
central metal atom and the ligands. But they differ in the
spatial arrangement of ligands in three dimensional
space.
 They can be further classified as
 Geometrical isomers
 Optical isomers.
Geometrical isomers:
 Geometrical isomerism exists in heteroleptic complexes due to
different possible three dimensional spatial arrangements of the
ligands around the central metal atom.
 This type of isomerism exists in square planer and octahedral
complexes.
Square planar complex - MA2B2 , MA2BC , M(xy)2 , MABCD - isomers

MA2B2 :

Example [ Pt(NH3)2Cl2]2+
MA2BC :

Example : [Pt(NH3)2 Cl Br]2+

M(xy)2 :

Example: [Pt(NH2 - CH2 – COO)2 ]

MABCD

Example: [ Pt NH3 Br Cl NO2 ]

Octahedral complexes:
 Octahedral complexes of the type [MA2B4]n±, [M(xx)2B2]n± shows
cis-trans isomerism.
 Here A and B are monodentate ligands and xx is bidentate ligand
with two same kind of donor atoms. In the octahedral complex, the
position of ligands is indicated by the following numbering scheme.
 In the above scheme, the
positions (1,2), (1,3), (1,4), (1,5),
(2,3), (2,5), (2,6), (3,4), (3,6),(4,5),
(4,6), and (5,6) are identical and
if two similar groups are present
in any one of these positions,
the isomer is referred as a cis-
isomer.
 Similarly, positions (1,6), (2,4),
and (3,5) are identical and if
similar ligands are present in
these positions it is referred as a
trans-isomer.
Octahedral complex of the type [MA3B3]n± also shows
geometrical isomerism. If the three similar ligands (A) are
present in the corners of one triangular face of the
octahedron and the other three ligands (B) are present in the
opposing triangular face, then the isomer is referred
as a facial isomer (fac isomer)
 If the three similar ligands are present around the
meridian which is an imaginary semicircle from one apex
of the octahedral to the opposite apex as shown in the
figure. the isomer is called as a meridional isomer
(mer isomer).
 This is called meridional because each set of ligands can
be regarded as lying on a meridian of an octahedron.
As the number of different ligands
increases, the number of possible
isomers also increases. For the
octahedral complex of the type
[MABCDEF]n±, where A, B, C, D, E and F
are monodentate ligands, fifteen
different orientation are possible
corresponding to 15 geometrical
isomers.
It is difficult to generate all the
possible isomers.
Fac and Mer Stereoisomers:
When three identical ligands occupy one face of an
octahedron, the isomer is said to be facial, or fac. In a
fac isomer, any two identical ligands are adjacent or cis to
each other. If these three ligands and the metal ion are in
one plane, the isomer is said to be meridional, or mer.
Theories of coordination compound
 Alfred Werner considered the bonding in coordination compounds
as the bonding between a lewis acid and a lewis base.
 His approach is useful in explaining some of the observed
properties of coordination compounds.
 However, properties such as colour, magnetic property etc.. of
complexes could not be explained on the basis of his approach.
 Following werner theory, Linus pauling proposed the Valence Bond
Theory (VBT) which assumes that the bond formed between the
central metal atom and the ligand is purely covalent.
 Bethe and Van vleck treated the interaction between the metal ion
and the ligands as electrostatic and extended the Crystal Field
Theory (CFT) to explain the properties of coordination compounds.
 Further, Ligand field theory and Molecular orbital have been
developed to explain the nature of bonding in the coordination
compounds.
 In this porton we learn the elementry treatment of VBT and CFT to
simple coordination compounds.
 Valence Bond Theory
 Linus pauling proposed the
Valence Bond Theory (VBT)
which assumes that the bond
formed between the central
metal atom and the ligand is
purely covalent.

According to this theory, the bond formed between

the central metal atom and the ligand is due to the
overlap of filled ligand orbitals containing a lone
pair of electron with the vacant hybrid orbitals of
the central metal atom.
Main assumptions of VBT:
1. The ligand → metal bond in a coordination complex is
covalent in nature. It is formed by sharing of electrons
(provided by the ligands) between the central metal atom
and the ligand.
2. Each ligand should have at least one filled orbital
containing a lone pair of electrons.

3. In order to accommodate the electron pairs donated by

the ligands, the central metal ion present in a complex
provides required number (coordination number) of vacant
orbitals.
4. These vacant orbitals of central metal atom undergo
hybridisation, the process of mixing of atomic orbitals of
comparable energy to form equal number of new orbitals
called hybridised orbitals with same energy.
5. The vacant hybridised orbitals of the central metal ion,
linearly overlap with filled orbitals of the ligands to form
coordinate covalent sigma bonds between the metal and
the ligand.
6. The hybridised orbitals are directional and their orientation in
space gives a definitengeometry to the complex ion.
7. In the octahedral complexes, if the (n-1) d orbitals are involved in
hybridisation, then they are called inner orbital complexes or low
spin complexes or spin paired complexes. If the nd orbitals are
involved in hybridisation, then such complexes are called outer
orbital or
high spin or spin free complexes. Here n represents the principal
quantum number of the outermost shell.
8. The complexes containing a central metal atom with
unpaired electron(s) are paramagnetic . If all the electrons
are paired, then the complexes will be diamagnetic.

9. Ligands such as CO, CN- , en, and NH present in the

3

complexes cause pairing of electrons present in the central

metal atom. Such ligands are called strong field ligands.

10. Greater the overlapping between the ligand orbitals

and the hybridised metal orbital, greater is the bond
strength.
Illustration 1
Limitations of VBT
Eventhough VBT explains many of the observed properties of
complexes, it still has following limitations
1. It does not explain the colour of the complex
2. It considers only the spin only magnetic moments and does not
consider the other components of magnetic moments.
3. It does not provide a quantitative explanation as to why certain
complexes are inner orbital complexes and the others are outer
orbital complexes for the same metal. For example, [Fe(CN)6]4- is
diamagnetic (low spin) whereas [FeF6]4- is paramagnetic (high spin).
The salient features of CFT
1. Crystal Field Theory (CFT) assumes that the bond between the
ligand and the central metal atom is purely ionic. i.e. the bond is
formed due to the electrostatic attraction between the electron rich
ligand and the electron deficient metal.
2. In the coordination compounds, the central metal atom/ion and
the ligands are considered as point charges (in case of charged metal
ions or ligands) or electric dipoles (in case of metal atoms or neutral
ligands).
3. According to crystal field theory, the complex formation is
considered as the following series of hypothetical steps.
Step 1:
In an isolated gaseous state, all the five d orbitals of the central metal ion are
degenerate. Initially, the ligands form a spherical field of negative charge around
the metal. In this field, the energies of all the five d orbitals will increase due to the
repulsion between the electrons of the metal and the ligand.
Step 2:
The ligands are approaching the metal atom in actual bond directions. To
illustrate this let us consider an octahedral field, in which the central metal ion is
located at the origin and the Six ligands are coming from the +x, -x, +y, -y, +z
and -z directions as shown below.
As shown in the figure, the orbitals lying along the axes dx2-y2 and
dz2 orbitals will experience strong repulsion and raise in energy to a
greater extent than the orbitals with lobes directed between the axes
(dxy, dyz and dzx). Thus the degenerate d orbitals now split into two
sets and the process is called crystal field splitting.

Step 3:
Up to this point the complex formation would not be favoured.
However, when the ligands approach further, there will be an
attraction between the negatively charged electron and the positively
charged metal ion, that results in a net decrease in energy.
This decrease in energy is the driving force for the complex
formation.
Crystal field splitting in octahedral complexes:
 During crystal field splitting in octahedral field, in order to
maintain the average energy of the orbitals (bary centre)
constant, the energy of the orbitals dx2-y2 and dz2 (represented as
eg orbitals) will increase by 3/5Δo while that of the other three
orbitals dxy, dyz and dzx (represented as t2g orbitals) decrease by
2/5Δo. Here, Δo represents the crystal field splitting energy in the
octahedral field.
Crystal field splitting in tetrahedral complexes:
The approach of ligands in tetrahedral field can be visualized as
follows. Consider a cube in which the central metal atom is placed at
its centre (i.e. origin of the coordinate axis as shown in the figure).
The four ligands approach the central metal atom along the
direction of the leading diagonals drawn from alternate corners of
the cube.
Crystal filed splitting Energy and nature of ligands:
• The magnitude of crystal field splitting energy not only depends
on the ligand field as discussed above but also depends on the
nature of the ligand, the nature of the central metal atom/ion and
the charge on it.
• Let us understand the effect of the nature of ligand on crystal
field splitting by calculating the crystal field splitting energy of
the octahedral complexes of titanium(III) with different ligands
such as fluoride, bromide and water using their absorption
• spectral data.. wave numbers of complexes [TiBr6]3- , [TiF6]3-
The absorption
and [Ti(H2O)6]3+ are 12500, 19000 and 20000 cm-1 respectively.
• The energy associated with the absorbed wave numbers of the
light, corresponds to the crystal field splitting energy (Δ) and is
given by the following expression,

• where h is the Plank' s constant; c is velocity of light, υ is the wave number of

absorptionmaximum which is equal to 1/λ.
• From the above calculations, it is clear that the crystal filed
splitting energy of the Ti 3+ in complexes, the three ligands is in
the order; Br- < F- < H2O. Similarly, it has been found form the
spectral data that the crystal field splitting power of various
ligands for a given metal ion, are in the following order

• The above series is known as spectrochemical series. The ligands

present on the right side of the series such as carbonyl causes
relatively larger crystal field splitting and are called strong
ligands or strong field ligands, while the ligands on the left side
are called weak field ligands and causes relatively smaller crystal
field splitting.
Distribution of d electrons in octahedral complexes:
• The filling of electrons in the d orbitals in the presence of ligand
field also follows Hund’s rule.

• In the octahedral complexes with d2 and d3 configurations, the

electrons occupy different degenerate t2g orbitals and remains
unpaired.
• In case of d4 configuration, there are two possibilities.

• The fourth electron may either go to the higher energy eg orbitals

or it may pair with one of the t2g electrons.

• In this scenario, the preferred configuration will be the one with

lowest energy.

• If the octahedral crystal field splitting energy (Δo) is greater than

the pairing energy (P), it is necessary to cause pairing of electrons
in an orbital, then the fourth electron will pair up with an the
electron in the t2g orbital.

• Conversely, if the Δo is lesser than P, then the fourth electron will

occupy one of the degenerate higher energy eg orbitals.
 "Pairing energy, P, is
the energy required to
place two electrons in
the same orbital. If the
crystal field splitting (Δ)
is small because of
weak-bonding ligands,
then the pairing
energy will be larger,
and the complex will be
high-spin.
Colour of the complex and crystal field splitting energy:
• Most of the transition metal complexes are coloured.
• A substance exhibits colour when it absorbs the light of a
particular wavelength in the visible region and transmit the rest
of the visible light.
• When this transmitted light enters our eye, our brain recognizes
its colour.
• The colour of the transmitted light is given by the
complementary colour of the absorbed light.

Colour Wheel - Complementary

colours are shown on opposite
sides
 For example, the hydrated copper(II) ion is blue in colour as it
absorbs orange light, and transmit its complementary colour,
blue.

 A list of absorbed wavelength and their complementary colour is

given in the following table
• The observed colour of a coordination compound can be
explained using crystal field theory.
• We learnt that the ligand field causes the splitting of d orbitals of
the central metal atom into two sets (t2g and eg).
• When the white light falls on the complex ion, the central metal
ion absorbs visible light corresponding to the crystal filed
splitting energy and transmits rest of the light which is
responsible for the colour of the complex.
• This absorption causes excitation of d-electrons of central metal
ion from the lower energy t2g level to the higher energy eg level
which is known as d-d transition.
• Let us understand the d-d transitions by considering [Ti(H2O)6] 3+ as an
example.
• In this complex the central metal ion is Ti 3+ , which has d1 configuration.
• This single electron occupies one of the t2g orbitals in the octahedral aqua ligand
field.
• When white light falls on this complex the d electron absorbs light and
promotes itself to eg level.
• The spectral data show the absorption maximum
is at 20000 cm-1 corresponding to the crystal field
splitting energy (Δo) 239.7 kJ mol-1 .

• The transmitted colour associated with this

absorption is purple and hence ,the complex
appears purple in colour.
 The octahedral titanium(III) complexes with other

ligands such as bromide and fluoride have different

colours.

 This is due to the difference in the magnitude of crystal

field splitting by these ligands.

 However, the complexes of central metal atom such as

of Sc3+ , Ti4+ , Cu+ , Zn2+ , etc... are colourless.

 This is because the d-d transition is not possible in

Metallic carbonyls
Classification:
• Generally metal carbonyls are classified in two different ways as
described below.
Other examples of this type are,Tc2(CO)10, and
Re2(CO)10.
 In metal carbonyls, the bond between metal atom and the
carbonyl ligand consists of two components.
 The first component is an electron pair donation from the carbon
atom of carbonyl ligand into a vacant d-orbital of central metal
atom.
 This electron pair donation forms M O sigma bond.

 This sigma bond formation increases the electron density in metal

d orbitals and makes the metal electron rich.

 In order to compensate for this increased electron density, a filled

metal d-orbital interacts with the empty π* orbital on the
carbonyl ligand and transfers the added electron density back to
the ligand.

 This second component metal through sigma bonding and from

metal to ligand through pi bonding, this synergic effect accounts
for strong M CO bond in metal carbonyls.
Stability of metal complexes:
 The stability of coordination complexes can be
interpreted in two different ways.
 The first one is thermodynamic stability and second one
is kinetic stability.
 Thermodynamic stability of a coordination complex
refers to the free energy change (ΔG) of a complex
formation reaction.
 Kinetic stability of a coordination complex refers to the

ligand substitution.
 In some cases, complexes can undergo rapid ligand
substitution; such complexes are called labile complexes.
 However, some complexes undergo ligand substitution
very slowly (or sometimes no substitution), such
Stepwise formation constants and overall formation constants:
 When a free metal ion is in aqueous medium, it is surrounded by
(coordinated with) water molecules.
 It is represented as [MS6]. If ligands which are stronger than
water are added to this metal salt solution, coordinated water
molecules are replaced by strong ligands.
Importance and applications of coordination complexes:
The coordination complexes are of great importance. These compounds are
present in many plants, animals and in minerals. Some Important applications of
coordination complexes are described below.
1.Phthalo blue – a bright blue pigment is a complex of Copper (II)
ion and it is used in printing ink and in the packaging industry.

2. Purification of Nickel by Mond’s process involves formation

[Ni(CO)4], which Yields 99.5% pure Nickel on decomposition.
3. EDTA is used as a chelating ligand for the separation of
lanthanides , in softening of hard water and also in removing lead
poisoning.

4. Coordination complexes are used in the extraction of silver and

gold from their ores by forming soluble cyano complex. These cyano
complexes are reduced by zinc to yield metals. This process is called
as Mac-Arthur –Forrest cyanide process.
5. Some metal ions are estimated more accurately by complex
formation. For example, Ni2+ ions present in Nickel chloride
solution is estimated accurately for forming an insoluble complex
called [Ni(DMG)2].
6. Many of the complexes are used as catalysts in organic and
inorganic reactions.
For example,
(i) Wilkinson’s catalyst – [(PPh3)3 RhCl] is used for hydrogenation of
alkenes.

(ii) Ziegler-Natta catalyst – TiCl4 + Al(C2 H5 )3 is used in the

polymerization of ethene.
7. In order to get a fine and uniform deposit of superior metals (Ag,
Au, Pt etc.,) over base metals, Coordination complexes [Ag (CN)2]- and
[Au(CN)2]- etc., are used in electrolytic bath.
8. Many complexes are used as medicines for the treatment of various
diseases. For example,
(1) Ca-EDTA chelate, is used in the treatment of lead and radioactive
poisoning. That is for removing lead and radioactive metal ions
from the body.

(2) Cis-platin is used as an antitumor drug in cancer treatment.

9. In photography, when the developed film is washed with sodium
thio sulphate solution (hypo), the negative film gets fixed.
Undecomposed AgBr forms a soluble complex called
sodiumdithiosulphatoargentate(I) which can be easily removed by
washing the film with water.

AgBr + 2 Na2S2O3 Na3 [Ag(S2O3)2 + 2 NaBr

10. Many biological systems contain metal complexes. For example,
(i)A red blood corpuscles (RBC) is composed of heme group, which
is
Fe2+ - Porphyrin complex.it plays an important role in carrying
oxygen from lungs to tissues and carbon dioxide from tissues to
lungs.
(ii) Chlorophyll, a green pigment present in green plants and algae,
is a coordination complex containing Mg2+ as central metal ion
surrounded by a modified Porphyrin ligand called corrin ring. It
plays an important role in photosynthesis, by which plants converts
CO2 and water into carbohydrates and oxygen.
(iii) Vitamin B (cyanocobalamine) is the only vitamin
12

consist of metal ion. it is a coordination complex in which

the central metal ion is Co+ surrounded by Porphyrin like
ligand.
(iv) Many enzymes are known to be metal complexes, they regulate
biological processes. For example, Carboxypeptidase is a protease
enzyme that hydrolytic enzyme important in digestion, contains a
zinc ion coordinated to the protein.
UTHRAKUMAR B
PGT CHEMISTRY
VELAMMAL MATRIC HR SEC
SCHOOL-SURAPET,CHENNAI
9790815359