COORDINATION

COMPOUND
• Coordination compounds are chemical compounds that
consist of an array of anions or neutral molecules that are
bound to a central atom via coordinate covalent bonds.

• Coordination compounds are also referred to

as coordination complexes. These molecules or ions that
are bound to the central atom are referred to as ligands
 CO-ORDINATION ENTITY:
The central metal atom or ion along with ligands form a co-
ordination entity. For example, [CoCl3(NH3)3] is a co-
ordination 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+
.
 CENTRAL ATOM/ION:
• In a co-ordination entity, the atom/ion to which a fixed number
of ions/neutral molecules are attached is called the central atom
or ion. For example, the central atom/ion in the co-ordination
entities:
• [NiCl2(H2O)4] - Ni2+,
2+
• [CoCl(NH3)5] - Co3+
3–
• [Fe(CN)6] Fe3+

• These central atoms/ions are also referred to as Lewis acids,

since they accept electron pairs from ligands.
 LIGANDS:
The negative ions or neutral molecules which are bonded to the
central atom/ion in the coordination entity are called ligands. For a
species to act as ligand, it can donate at least one pair of electron
to the central atom. Examples for ligands are Cl- , Br- , F- , I- , OH- ,
CN- , NC- , CNO- , NCO- , SO4 2-
, NO3 - , CNS-, H2O, NH3, CO etc

The atom of the ligand which is directly bonded to the central

atom or ion is called co-ordinating atom or donor atom. For
example in the ligand NH3, Nitrogen is the co-ordinating atom
(donor atom).
Types of ligands
Based on the number of donor atoms of the ligand that binds to a
metal ion or atom, the ligands are classified as follows:
a) Monodentate or unidentate ligand: A ligand that binds to
the central atom/ion through a single donor atom, is said to be
unidentate ligand. E.g.: Cl-, Br-, I-, OH-, H2O, NH3, CN-, NC-, SCN- etc.

b) Bidentate (Didentate) ligands: A ligand that binds to the

central atom through two donor atoms is called a bidentate ligand.
E.g.: Ethane-1,2-diamine or ethylenediamine (H2NCH2CH2NH2)
notated as ‘en’ (C2O4 2–).
c) Polydentate ligand: A ligand that binds to the central atom
through more than two donor atoms is called polydentate ligand
E.g.: Triethylamine ammonia [N(CH2-CH2-NH2)3], Ethylenediamine
tetraacetate ion (EDTA4–) etc. Ethylenediamine tetraacetate ion
(EDTA4–) is an important hexadentate ligand. It can bind to the
central atom through two nitrogen and four oxygen atoms
Ambidentate Ligand
• Ambidentate Ligand which can ligate through two different atoms
is called ambidentate ligand. e.g., NO2−,SCN− ions.

• NO2− ion can coordinate either through nitrogen or through

oxygen to a central metal atom/ion.
Chelating Ligands:

• Di- or polydentate ligands can bind to the central atom through

two or more donor atoms and form ring complexes. Such
complexes are called chelates and such types of ligands are said
to be chelating ligands.
• Complexes containing chelating ligands are more stable than
those containing unidentate ligands.
• For e.g. the complex [Co(en)3]3+ is a chelate and ethane-1,2-
diamine (en) is a chelating ligand
Denticity:
• The number of donor atoms of a particular ligand that are directly
bonded to the central atom is called denticity.
• For unidentate ligands, the denticity is 1, for didentate ligands it is 2
and so on
Co-ordination number:
• The co-ordination number (C.N) of a metal ion in a complex is the
total number of ligand donor atoms to which the metal is directly
bonded.
• It is determined only by the number of sigma bonds formed by the
ligand with the central atom/ion.
• For example,
• In the complex ion [PtCl6] 2–
the co-ordination number of Pt is 6.
• [Ni(NH3)4] 2+
, the co-ordination number of Ni is 4.

• In the complex ions, [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 bidentate ligands.

• Generally, the co-ordination number of most of the complexes is
2, 4 or 6
Co-ordination sphere:

• The central atom/ion and the ligands attached to it are

enclosed in square bracket and is collectively termed as the co-
ordination sphere.
• The ionisable groups are written outside the bracket and are
called simple ions or counter ions.

• For example, in the complex K4[Fe(CN)6], the coordination

sphere is [Fe(CN)6] 4–
and the counter ion is K+
Co-ordination polyhedron:
• The spatial arrangement of the ligands around the central
atom/ion defines a co-ordination polyhedron about the central
atom.
• The most common co-ordination polyhedra are octahedral, square
planar and tetrahedral. For example, [Co(NH3)6] 3+ is octahedral,
[Ni(CO)4] is tetrahedral and [PtCl4] 2–
is square planar.
Oxidation number of central atom:
• The oxidation number of the central atom in a complex is defined
as the residual charge on it, if all the ligands are removed along
with their electron pairs that are shared with the central atom.
• The oxidation number is represented by a Roman numeral in
simple brackets. For example, oxidation number of copper in
[Cu(CN)4] 3– is +1 and it is written as Cu(I).

• [Co(NH3)6] 3+

• [PtCl4] 2–

• [Ni(CO)4]
Homoleptic and Heteroleptic complexes:

• Complexes which contain only one type of ligand are called

homoleptic complexes.
E.g.: [Co(NH3)6] 3+, [Fe(CN)6] 4- etc.

• Complexes which contain more than one type of ligands are called
heteroleptic complexes.
E.g., [Co(NH3)4Cl2] + , [Cu(NH3)2Cl2] etc
IUPAC NOMENCLATURE OF CO-ORDINATION COMPOUNDS

The following rules are used while naming co-ordination compounds:

• The cation is named first in both positively and negatively charged
co-ordination entities.
• The ligands are named in alphabetical order before the name of the
central atom/ion.
• Names of the anionic ligands end in –o, those of neutral and cationic
ligands are the same except ‘aqua’ for H2O, ‘ammine’ for NH3,
‘carbonyl’ for CO and ‘nitrosyl’ for NO.
• Prefixes mono, di, tri, etc., are used to indicate the number of
individual ligands. When the names of the ligands include a
numerical prefix, then the terms bis (for 2 such ligands), tris (for 3),
tetrakis (for 4) are used. Here the name of the ligand is placed in
simple bracket.
• Oxidation state of the metal is indicated by Roman numeral in simple
bracket.
• If the complex ion is a cation, the central atom is named same as the
element. If the complex ion is an anion, the name of the metal ends
with the suffix –ate. For example ferrate for iron, cobaltate for cobalt,
zincate for Zn etc.
• The neutral complexes are named similar to cationic complexes.
(3x+1)+(X)+(-1x6)=0 Tetracarbonylnickel(0)
3+X+-6=0
X=6-3=3
Potassium hexacyanidoferrate(III) Hexaamminecobalt(III) chloride

(+1x2)+X+(-1x4)=0 Pentaamminechloridocobalt(III)
chloride
2+X+(-4)=0 X=2
Potassium tetrahydroxidozincate(II)
Dichloridobis(ethane-1,2-diamine)cobalt(III) chloride
Formulas of Mononuclear Co-ordination Entities

The following rules are used while writing the formulas:

• The central atom is listed first.
• The ligands are then listed in alphabetical order.
• The formula for the entire coordination entity is enclosed in
square brackets. When ligands are polyatomic, their formulas
are enclosed in bracket.
• There should be no space between the ligands and the
metal within a coordination sphere.

• For complex ions, the charge is indicated outside the

square brackets as a right superscript with the number
before the sign.

• The charge of the cation(s) is balanced by the charge of

the anion(s)
• Isomerism in Co-ordination Compounds
• Compounds that have the same molecular formula but different
structural formula or spatial arrangement of atoms are called
isomers and the phenomenon is called isomerism.
• Isomers differ in physical or chemical properties.
• The isomerism shown by co-ordination compounds are broadly
divided into two – structural isomerism and stereo isomerism
I) Structural Isomerism
• These are isomers which differ in the structural arrangement of
ligands around the central atom. They are of four types:

1) Ionisation Isomerism:
• It arises due to the inter change of ions between the inside and
outside of the co-ordination sphere.
• They give different types of ions in aqueous solution. In order to
show this isomerism, the ion outside the co-ordination sphere can
also act as ligand.
• E.g.: [Co(NH3)5SO4]Br and [Co(NH3)5Br]SO4,

• [Pt(NH3)3Cl]Br and [Pt(NH3)3Br]Cl

2) Solvate isomerism:
• It arises due to the difference in the no. of solvent molecule
which are directly bonded to the metal ion as ligand.
• It is similar to ionisation isomerism.
• If water is the solvent, this isomerism is also known as ‘hydrate
isomerism’.
• An example is [Cr(H2O)6]Cl3 (violet) and its solvate isomer
[Cr(H2O)5Cl]Cl2.H2O (grey-green).
3) Linkage isomerism:
• It arises in a co-ordination compound containing ambidentate
ligand, which can bind to the central atom through more than
one donor atoms.

• For example complexes containing thiocyanate ligand, SCN– ,

may bind either through nitrogen to give M–NCS or through
sulphur to give M– SCN.

• Another e.g. is [Co(NH3)5(ONO)]Cl2, in which the nitrite ligand is

bound through oxygen (–ONO), and [Co(NH3)5(NO2)]Cl2 in which
the nitrite ligand is bound through nitrogen (–NO2).
4) Co-ordination Isomerism:

• If both anionic and cationic parts of a complex are in complex

form, the isomerism arises due to the interchange of ligands
between cationic and anionic entities.

• This type of isomerism is called co-ordination isomerism.

• An example is [Co(NH3)6][Cr(CN)6], in which the NH3 ligands are

bound to Co3+ and the CN– ligands to Cr3+ and [Cr(NH3)6]
[Co(CN)6], the NH3 ligands are bound to Cr3+ and the CN– ligands
to Co3+ .
II) Stereoisomerism
• These are isomers which differ only in the spatial arrangement
of ligands around the central atom. They have same atom to
atom bond. These are of two types:

(i) Geometrical isomerism

(ii) Optical isomerism
i) Geometrical Isomerism:
• This type of isomerism is shown by complexes.
• It arises due to the different possible geometric arrangements
of the ligands around the central atom.
• Isomer in which the same ligands are on the same side of the
central metal atom is called cis isomer and the isomer in which
the same ligands are on the opposite side is called trans
isomer.
• This isomerism is mainly found in heteroleptic complexes with
co-ordination numbers 4 (square planar complexes) and 6
(octahedral complexes).
• Square planar complexes with formula [MX2L2] (X and L are
unidentate ligands) can show this isomerism. E.g.:
[Pt(NH3)2Cl2]
• Octahedral complexes with formula [MX2L4] can also show this
type of isomerism.
• Here the two ligands X may be oriented cis or trans to each
other.
• This type of isomerism also arises when bidentate ligands (L –
L) are present in complexes with formula [MX2(L – L)2] e.g.: [Co
(en)2Cl2] +
Fac-mer isomerism:
• It is a type of geometrical isomerism occurs in octahedral co-
ordination entities of the type [Ma3b3].
• If similar ligands occupy three adjacent positions of an
octahedral face, it is called facial (fac) isomer.
• When the positions are around the meridian of the octahedron,
it is called meridional (mer) isomer
• Eg. [Co(NH3)3(NO2)3]
ii) Optical Isomerism
• Optical isomers are mirror images that cannot be superimposed
on one another. These are also called enantiomers.
• The molecules or ions that cannot be superimposed are called
chiral. There are two forms of optical isomers - dextro (d) and
laevo (l) depending on the direction they rotate the plane of
polarised light in a polarimeter.
• The isomer which rotates the plane polarized light towards right
are called dextro (d) isomer and that rotates to left are called
laevo(l) isomer
• Optical isomerism is common in octahedral complexes involving
bidentate ligands. In a co-ordination entity of the type [PtCl 2(en)2]
2+
, only the cis-isomer shows optical activity. The trans- isomer
has a plane of symmetry and is optically inactive.
 Theories of Co-ordination Compounds
1) Werner’s Co-ordination Theory
The first theory related to co-ordination compounds was proposed
by Alfred Werner. He studied the aminocomplexes of Co, Pt etc.
and proposed the following postulates:
Every metal has two types of valencies – primary (10 ) valency
and secondary (20 ) valency. Primary valency is ionisable, while
secondary valency is non-ionisable.
Primary valency is denoted by doted lines, while secondary
valency is denoted by thick lines.
Primary valency gives the oxidation state of the metal, while
secondary valency gives the co-ordination number of the metal
 The Valence Bond Theory (VBT)
• This theory was put forward by Linus Pauling. The important
postulates of this theory are:
• In co-ordination compounds, the central metal atom/ion provides
some vacant orbitals in order to accommodate the electrons
donated by the ligands.

• The number of vacant orbitals formed is equal to the co-

ordination number of the metal atom.

• The vacant orbitals of the metal undergo hybridisation to form a

set of new orbitals called hybrid orbitals. The type of
hybridisation gives the shape of the compound.
• Tetrahedral, square planar and octahedral complexes are
formed as a result of sp3 dsp2 and d2sp3(sp3d2 )
hybridisation respectively.

• Each ligand should contain at least one pair of electron.

• The vacant hybrid orbitals of the metal overlap with the filled
orbitals of the ligands to form ligand – metal co-ordinate
bond.

• If a complex contains unpaired electron, it is paramagnetic

and if it contains only paired electron, it is diamagnetic
• APPLICATIONS OF VBT
• It is usually possible to predict the geometry of a complex from
the knowledge of its magnetic behavior on the basis of the
valence bond theory.
1. [Co(NH3)6] 3+

Central atom Cobalt is in +3 oxidation state.

27 Co [Ar]3d 4s7 2

Co 3+ [Ar]3d 4s 4p
6 0 0

Orbital of Co3+
1. [Co(NH3)6] 3+

Central atom Cobalt is in +3 oxidation state.

27 Co – [Ar]3d7 4s2

Co3+ – [Ar]3d6 4s04p0

Orbital of Co3+
• Co-ordination number of Co is 6 (total number of ligand donor
atoms to which the metal is directly bonded.)

• Hence the no. of vacant orbitals required = 6.

• In presence of the ligand NH3, the electrons in 3d level get

paired. Now the two 3d orbitals, one 4s orbital and three 4p
orbitals undergo d2 sp3 hybridization to form 6 new orbitals.

• Since the hybridization is d2sp3 ,

• The shape of the molecule is octahedral

d2sp3 hybridized orbital
of Co3+

Six pairs of electrons, one from each NH3, occupy these six hybrid
orbitals.
[Co(NH3)6] 3+
Inner orbital or low spin
complex

Due to the absence of unpaired electron, the complex is

diamagnetic.
In the formation of this complex, since the inner d orbitals (3d)
are used for hybridization, the complex is called an inner orbital
or low spin or spin paired complex.
2. [CoF6] 3-
Central atom cobalt is in +3 oxidation state.

27 Co – [Ar]3d7 4s2

Co3+ - [Ar]3d6 4s04p0

• Co-ordination number of Co = 6
• The no. of vacant orbitals required = 6.
• In presence of the ligand F – the electrons in 3d level do not
get paired.
• So, one 4s orbital, three 4p orbitals and two 4d orbitals
undergo sp3d2 hybridization to form 6 new orbitals. Since the
hybridisation is sp3d2
• Shape of the complex is octahedral
These hybrid orbitals overlap with the filled orbitals of the ligand to
form ligand– metal co-ordinate bond
• Due to the presence of 5 unpaired electrons, it is highly
paramagnetic.
• Since the outer d-orbitals (4d ) are used for hybridisation
(sp3d2), this complex is called outer orbital or high spin or
spin free complex.
[Ni(CN)4]2-

Atomic number=28

CN- is a strong ligand

3. [Ni(CN)4]2-

Central atom- Ni is in +2 oxidation state.

28 Ni – [Ar]3d84s2
2+
Ni - [Ar]3d8 4s04p0

Co-ordination number of Ni is 4 and hence the no. of vacant orbitals

required = 4.
Even though it contains 4 orbitals, in presence of the ligand CN - the
electrons in 3d level get paired.
One 3d orbital, one 4s orbital and two 4p orbitals undergo dsp2
hybridization to form 4 new orbitals.
Four pairs of electrons, one from each CN-ions, occupy these four
hybrid orbitals

The complex has square planar geometry and is diamagnetic,

because of the absence of unpaired electron.
4. [NiCl4]2-

• The central atom Ni is in +2 oxidation state.

8 2
28Ni – [Ar]3d 4s
2+
Ni - [Ar]3d8 4s04p0

Co-ordination number of Ni -4
hence the no. of vacant orbitals required = 4.

In presence of the ligand Cl- the electrons in 3d level do not get paired
Now the one 4s orbitals and three 4p orbitals undergo sp3 hybridization to
form 4 new orbitals.
• These four hybrid orbitals are occupied by the four electron pairs from
each Cl-ligands.

Thus, the complex has tetrahedral geometry and is paramagnetic

because of the presence of unpaired electron.
•Limitations of Valence Bond Theory

• VB theory explains the formation, structure and magnetic

behaviour of co-ordination compounds, it has the following
limitations:

• It involves a large number of assumptions.

• It does not give quantitative interpretation of magnetic

data of complexes.

• It does not explain the colour exhibited by co-ordination

compounds.
• It does not give a quantitative interpretation of the
thermodynamic or kinetic stabilities of co-
ordination compounds.

• It does not make exact predictions regarding the

tetrahedral and square planar structures of 4-co-
ordinated complexes.

• It does not distinguish between weak and strong

ligands.
• WERNER’S CO-ORDINATION THEORY
• The first theory related to co-ordination compounds was
proposed by Alfred Werner. He studied the
aminocomplexes of Co, Pt etc. and proposed the following
postulates:
 Every metal has two types of valencies – primary (10)
valency and secondary (20) valency. Primary valency is
ionisable, while secondary valency is non-ionisable.

Primary valency is denoted by doted lines, while

secondary valency is denoted by thick lines.

Primary valency gives the oxidation state of the metal,

Primary valency is always satisfied by –ve ions, while secondary
valency may be satisfied by -ve ions or neutral molecules.

Every metal has a fixed number of secondary valencies. In order to

satisfy this requirement, some – ve ions may perform dual character
– i.e., they act as primary and secondary valencies simultaneously.

The primary valencies are non-directional, while the secondary

valencies are directional. i.e. they are directed to some fixed
positions in space.

Since secondary valencies are directional, co-ordination compounds

have a definite geometry and they show isomerism.
CRYSTAL FIELD THEORY

 The crystal field theory (CFT) is an electrostatic model

which considers the metal-ligand bond as purely ionic.

 Here the ligands are treated as point charges in case of

anions or as dipoles in case of neutral molecules.

 The five d orbitals in an isolated gaseous metal atom/ion

have same energy, i.e., they are degenerate.
• This degeneracy is maintained if a spherically
symmetrical field of negative charges surrounds the metal
atom/ion. when this negative field is due to ligands in a
complex, it becomes asymmetrical and the degeneracy of
the d orbitals is lifted. It results in splitting of the d
orbitals. The pattern of splitting depends upon the nature
of the crystal field.

• It results in splitting of the d orbitals. This splitting of d-

orbitals is termed as Crystal field splitting and it depends
on the nature of the field
Crystal field splitting in octahedral co-
ordination entities (Octahedral splitting)

• In an octahedral co-ordination entity, there are six

ligands surrounding the metal atom/ion and they are
along the axis of the octahedron.

• So the repulsion between the electrons in metal d

orbitals and the electrons (or negative charges) of the
ligands is greater for the d x2-y2 and dz 2 orbitals, which
are pointing towards the axes, than the dxy, dyz and
dxz orbitals, which are directed between the axes.
• The energy of the dx2-y2 and dz2 orbitals
(called eg orbitals) will be raised and that
of the dxy , dyz and dxz orbitals (called t2g
orbitals) will be lowered.

• The degeneracy of the d orbitals has

been removed due to ligand electron-
metal electron repulsions

• This splitting of the degenerate levels due

to the presence of ligands in a definite
geometry is termed as crystal field
splitting and the energy separation is
denoted by Δo (the subscript o is for
octahedral).
The energy of the two eg orbitals will increase by 3/5 Δo
and that of the three t2g orbitals will decrease by 2/5 Δo.

Strong field ligands produce large splitting whereas weak

field ligands produce small splitting of d orbitals
• Filling of electrons
• For d1, d2 and d3 coordination entities, the d
electrons occupy the t2g orbitals singly in
accordance with the Hund’s rule. For d4 ions, two
possible patterns of electron distribution arise:

• The fourth electron could either enter the t2g

level and pair with an existing electron, or
• It could enter into the eg level.

• Here the electron distribution depends on the

relative magnitude of the crystal field splitting
(Δo) and the pairing energy (P).
• If Δo < P, the fourth electron enters one of
the eg orbitals giving the configuration t2g3eg 1.

• Ligands for which Δo < P are known as weak

field ligands and form high spin complexes.

• If Δo > P, the fourth electron occupy a t2g

orbital with configuration t2g4eg0.

• Ligands for which Δo < P are known as strong

field ligands and form low spin complexes
Crystal field splitting in tetrahedral co-
ordination entities (tetrahedral splitting)

A tetrahedron can be considered as a cube in

which only alternate corners are occupied by
ligands and the metal ion is at the centre of
the cube.

The dx2-y2 and dz2 orbitals (called e orbitals)

point towards the centre of each faces of the
cube and the dxy, dyz and dxz orbitals (called
t2 orbitals) point towards the edge centre of
the cube.
• Since the ligands are approaching through
the corners, there is no direct interaction
between the ligands and the d-orbitals.
However, the ‘t2’ (dxy, dyz and dxz )orbitals lie
closer to the ligands than the ‘e’ orbitals.

• As a result the energy of the ‘t2’ orbitals

increases and that of ‘e’ orbitals decreases.
So the d orbitals split into two – triply
degenerate ‘t2’ orbitals with higher energy
and doubly degenerate ‘e’ orbitals with
lower energy
• The splitting in tetrahedral
field is less than that in
octahedral field. It is found
that Δt = 4/9 Δo.

• This is because in tetrahedral

field, there are only four
ligands and there is no direct
interaction between the
ligands and the d-orbitals
• Spectrochemical series
• It is a series in which the ligands are arranged
in the increasing order of their field strength.
The series is: I-< Br- < SCN-< Cl- < S2- < F- < OH-
< C2 O4 2- < H2O < NCS– < edta4- < NH3 < en <
CN– < CO.

• It is an experimentally determined series based

on the absorption of light by complexes with
different ligands.
• Colour in Coordination Compounds

• Most of the complexes of transition metals are coloured. This

can be explained in terms of the crystal field theory.

• In presence of the ligands, the crystal field splitting occurs. So

the electrons from lower d level (t2g level) can excite to higher
d level (eg level). For this some energy is required, which is
absorbed from the white light.

• The colour of the complex is complementary to that which is

absorbed. Thus according to crystal field theory the colour of
the coordination compounds is due to d-d transition of the
• For example, the complex [Ti(H2O)6]3+ is violet in
colour.
• This is an octahedral complex where the single
electron (Ti3+ is a 3d1 system) in the metal d orbital
is in the t2g level in the ground state of the
complex.

• The next higher state available for the electron is

the empty eg level.

• If light corresponding to the energy of yellow-green

region is absorbed by the complex, it would excite
the electron from t2g level to the eg
level.Consequently, the complex appears violet in
• In the absence of ligand, crystal field splitting does not
occur and hence the substance is colourless.

• For example, when [Ti(H2O)6]3+ is heated it becomes

colourless. Similarly, anhydrous CuSO4 is white, but
CuSO4.5H2O is blue in colour.

• The colour of a complex depends on the strength of

ligand and the nature of the field.
• Limitations of Crystal Field Theory
• From the assumptions, that the ligands are point charges, it
follows that anionic ligands should exert the greatest
splitting effect. But the anionic ligands actually are found
at the low end of the spectrochemical series.

• It does not take into account the covalent character of

bonding between the ligand and the central atom.
Stability of Coordination Compounds
• The stability of a complex in solution refers to the
degree of association between the metal ion and
ligands in the state of equilibrium. The magnitude of
the (stability or formation) equilibrium constant for the
association, quantitatively expresses the stability.
• For a reaction of the type:
• M + 4L → ML4, β = [ML4]/[M][L]4
• As the value of the stability constant increases, the
stability of the complex also increases.
• The above reaction can be considered to take place in 4
steps:
• M + L → ML, K1 = [ML]/[M][L]
• ML + L → ML2, K2 = [ML2]/[ML][L]
• ML2 + L → ML3, K3 = [ML3]/[ML2][L]
• ML3 + L → ML4, K4 = [ML4]/[ML3][L]

• Where K1, K2,K3 and K4 are referred to as stepwise

stability constants.
• The overall stability constant, β = K1 × K2 × K3 × K4
• The stability of a complex depends on the following factors:
• The nature of the metal ion: Greater the charge to radius
of the metal ion, greater will be the stability of the complex.

• Nature of the ligand: The greater the basic strength of the

ligand, the greater will be the stability of the complex.

• Presence of chelating ligands: increases the stability of

the complex.
• Application of Co-ordination Complexes
• In Qualitative & Quantitative Analysis: Co-ordination
compounds find use in many qualitative and quantitative
chemical analyses. For e.g. Ni2+ is detected and estimated
by the formation of a complex with Dimethyl Glyoxime
(DMG).

• The brown ring test for the detection of nitrate ion is due
to the formation of the brown complex [Fe(H2O)5NO] 2+

• The Ca2+ and Mg2+ ions are estimated by the formation

of stable complexes with EDTA.
 In Metallurgy:
• Metals like silver and gold are extracted by the
formation of complexes with CN- ligands. Gold
forms the complex [Au(CN)2]- and silver forms
[Ag(CN)2]- which are separated with Zn.

• Similarly, co-ordination compounds also find

application in the refining of some metals. For
example, impure nickel is converted to [Ni(CO)4],
which is decomposed to yield pure nickel
• Biological Applications:
• Co-ordination compounds are of great importance
in biological systems. Chlorophyll is a co-
ordination compound of magnesium,
Haemoglobin, is a co-ordination compound of iron
and Vitamin B12 (cyanocobalamine) is a co-
ordination compound of cobalt.