9.

CO-ORDINATION COMPOUNDS

HAIZEL G. ROY
H.S.S.T. (HG) CHEMISTRY
GOVT. H.S.S. KALAMASSERY
ERNAKULAM.
 MOLECULAR OR ADDITION COMPOUNDS

Two or more stable compounds combined in stoichiometric proportions is

called molecular or addition compound.

Molecular compounds are of two types.

Double Salts
Coordination Compounds
 DOUBLE SALTS

These are addition compounds which lose their identity when dissolved in
water.
They exists in solid state.
Their properties are same as that of constituent compounds.
Eg. Mohr’s salt FeSO4 (NH4)2SO4.6H2O ; Potash alum : K2SO4Al2(SO4)3.24H2O

Eg. Carnallite KCl.MgCl2.6H2O dissolved in water, dissociates into K+ , Mg2+ , Cl−

and H2O.

Aqueous solution of Carnallite answer the tests for K+ , Mg2+ and Cl− ions.
 CO-ORDINATION COMPOUNDS

Addition compounds which retain their identity in solution.

They exist in solids as well as in solution.

K4[Fe(CN)6] does not form Fe2+ and CN − ions but forms [Fe(CN)6 ]4− ion.

Aqueous solution does not answer tests for individual ions like Fe2+ and CN− .
[Fe(CN)6]4− is known as the complex ion exist as a coordination entity.
TERMS OF COMMON USAGE IN
CO-ORDINATION CHEMISTRY
 CO-ORDINATION ENTITY

A central metal atom or ion surrounded by a fixed number of

oppositely charged ions or neutral molecules given in square
brackets is called Co-ordination Entity.
Eg. [Ni(CO)4], [Fe(CN)6]4− etc.
 COMPLEX ION

A Complex ion is an electrically charged species which consists of a

central metal ion surrounded by a group of ions or neutral molecules.

Eg. [Co(NH3)6]3+ , [Co(CN)6]3− etc.

 CATIONIC COMPLEX

A complex ion carrying a positive charge is called a Cationic Complex.

Eg. [Ni(NH3)6]2+ ,[Co(NH3)4]2+ ,[Co(NH3)4Cl2]+

 ANIONIC COMPLEX

A complex ion carrying a negative charge is called an Anionic

Complex.

Eg [PtCl6]2- , [Fe(CN)6]4- , [Fe(C2O4)3]3-

 NEUTRAL COMPLEX

A complex without any charge is called a Neutral Complex.

Eg [Ni(CO)4], [V(CO)5].
 CENTRAL ION

The cation to which one or more neutral molecules or anions are

attached to form a complex ion.

Eg. In the complex ion [Cu(NH3)4]2+ , Cu2+ ion is the central ion.
 LIGANDS

A species which is capable of donating electron pairs to the central

metal atom or ion is called a ligand.

It is a Lewis base.

Eg: NH3, H2O, CO, Cl-, CN- etc

 DENDICITY OF LIGANDS

The number of atoms through which the ligands can donate a pair of

electrons is called denticity of a ligand.

For example, denticity of ethane−1,2−diamine is 2.

Nitrogen has two donor nitrogen atoms which can donate electron

pairs to the central metal atom.

TYPES OF LIGANDS
 UNIDENDATE LIGANDS

A ligand bound to a metal ion through a single donor atom, is said to

be unidendate ligand.

Eg. NH3 , H2O, Cl − , Br − , OH − , CO etc.

 AMBIDENDATE LIGANDS

Unidendate ligands having two or more donor atoms but only one

donor atom is attached to the metal during complex formation.

 BIDENDATE LIGANDS

A ligand which can bind through two donor atoms, is said to be a

bidendate ligand.

Eg. H2N−CH2−CH2−NH2 , −OOC−COO − etc.

 POLYDENDATE LIGANDS

Ligands which have more than two donor atoms are called

polydendate ligands.

Eg: EDTA
 CHELATING LIGANDS

A bidendate or polydendate ligand which on coordination with the

same central metal atom forms a ring structure is called a chelating
ligand.
The complex having a ring structure is called a chelate.
 CHELATE

A metal complex formed by a chelating ligand is called a chelate.

The process of formation of a chelate is called chelation.

 COORDINATION NUMBER

The total number of monodendate ligands attached to the central

metal ion of a complex is called Co-ordination Number.

 COORDINATION SPHERE

The central metal ion and the ligands attached to it are enclosed in

square bracket are collectively termed as the coordination sphere.

Eg: K4[Fe(CN)6]
 COORDINATION POLYHEDRON


The spatial arrangements of the ligands which are directly attached

to the central metal ion is called coordination polyhedron.

 OXIDATION NUMBER OF CENTRAL ATOM


Oxidation number is the charge that the central atom would carry if

all the ligands are removed along with the electron pairs that are

shared with the central atom.

 HOMOLEPTIC AND HETEROLEPTIC COMPLEXES

Complexes in which a metal is bounded to only one kind of donor

groups are known as homoleptic complexes. Eg. [Co(NH3)6]3+

Complexes in which a metal is bound to more than one kind of donor

groups are known as heteroleptic complexes. Eg. [Co(NH3)4Cl2]+

 WERNER’S THEORY OF COORDINATION COMPOUNDS

The main postulates of this theory are

In coordination compounds metals show two types of valencies-1°and 2°.
The primary valences are normally ionisable and are satisfied by negative ions.
Primary valency is equal to the oxidation state of the central metal ion
The secondary valences are non ionisable.
These are satisfied by neutral molecules or negative ions.
The secondary valence is equal to the coordination number.
Secondary valences will determine the stereochemistry.
If the Co-Ordination Number is 4 it will be a Tetrahedral complex and if the Co-
Ordination Number is 6 it will be an Octahedral complex
 NOMENCLATURE OF COORDINATION COMPOUNDS

Name the positive ion first followed by negative ion.

Ligands are named first followed by metal ion.
Name the metal followed by its oxidation number in Roman numeral.
Negative ligands end in ‘O’. Eg. Chlorido, bromido, cyano etc.
Positive ligands end in ‘ium’. Eg. Nitronium, Nitrosonium etc.
Neutral ligands are named as such.
Eg; en-Ethylene diamine, H2O-aqua, CO-carbonyl, NO-nitrosyl, NH3 -ammine.
Ligands are named in their alphabetical order.

Indicate the number of ligands by prefixes di, tri, tetra etc.

Use the prefixes bis, tris, tetrakis etc for 2,3,4 in coordination entity for other

than unidentate ligands.

In ambidentate ligand, the symbol of the coordinated atom also included.

In neutral complexes, the name of the central metal ion is unchanged.

If the complex is a negative ion, the name of the metal ends in ‘ate’.
EXAMPLES
ANSWERS
EXAMPLES
ANSWERS
EXAMPLES
ANSWERS
 ISOMERISM
IN COORDINATION COMPOUNDS
 ISOMERISM IN COORDINATION COMPOUNDS

Compounds having the same molecular formula but different structural or

spatial arrangements are called isomers and the phenomenon is called
Isomerism.
If the isomerism is caused by the difference in the structure it is called
structural isomerism.
If the isomerism is caused by the difference in spatial arrangements, it is
called stereoisomerism.
A. STRUCTURAL ISOMERISM
 1. IONISATION ISOMERISM

This type of isomerism arises due to the exchange of ions between

the coordination sphere of the metal ion and ions outside the
coordination sphere.
Eg. [Co(NH3)5Br]SO4 and [Co(NH3)5SO4]Br
 2. HYDRATE ISOMERISM

This type of isomerism is due to the exchange of water between the

inside and outside of coordination sphere.
Eg. [Cr(H2O)6]Cl3

Eg: [Cr(H2O)5Cl]Cl2H2O and [Cr(H2O)4Cl2]Cl(H2O)2

 3. LINKAGE ISOMERISM

Certain ligands can donate the electron pair at two different sites and

the isomerism due to this is called linkage isomerism.

Eg. [Co(NH3)5NO2]Cl2 and [Co(NH3)5ONO]Cl2

 4. COORDINATION ISOMERISM

This occurs in compounds containing both cationic and anionic

complexes.
This isomerism is due to exchange of ligands in the coordination
sphere of cationic and anionic parts.
Eg. [Co(NH3)6][Cr(CN)6] and [Cr(NH3)6][Co(CN)6]
B. STEREO ISOMERISM
 STEREO ISOMERISM

This type of isomerism is due to the difference in spatial

arrangements of ligands around the central metal.
 1. GEOMETRICAL ISOMERISM

This type of isomerism is due to ligands occupying different positions

around the central metal.
When two identical ligands occupy adjacent positions, the isomer is
called cis isomer.
When two identical ligands occupy opposite positions the isomer is
called trans isomer.
 1. GEOMETRICAL ISOMERISM

Square planar complexes of the type MA2B2 and Octahedral

complexes of the type MA2B4 show geometrical isomerism.

EXAMPLES OF GEOMETRICAL ISOMERISM
EXAMPLES OF GEOMETRICAL ISOMERISM
Tetrahedral complex does not show geometrical isomerism because

the relative positions of unidentate ligands attached with central

metal atom are the same with respect to each other.

 2. OPTICAL ISOMERISM

This type of isomerism arises when a molecule of the complex is not

superimposable on its mirror image.

Eg. Octahedral complexes of the types [Co(en)3]3+ , [Co(en)2Cl2]2+

 EXAMPLES OF OPTICAL ISOMERISM

Optical isomers of [Co(en)3]3+ Optical isomers of [Co(en)2Cl2]2+

 OPTICAL ISOMERS OF Trans [Co(en)2Cl2 ]+

Trans [Co(en)2Cl2]+ does not show optical isomerism since it is

symmertric.
 BONDING IN COORDINATION COMPOUNDS

To explain the properties such as colour, geometry, magnetic

behaviour etc of complexes.
 VALENCE BOND THEORY (VBT)

This theory was proposed by Pauling.

The main assumptions of this theory are
The central metal atom in the complex provides a number of empty
orbitals for the formation of coordinate bonds with suitable ligands.
The number of empty orbitals provided is equal to the coordination
number of the central ion.
The atomic orbitals of the metal hybridise to form a set of equivalent
orbitals with definite geometry such as square planar, tetrahedral,
octahedral etc.
The empty hybrid orbitals of metal ion overlap with the filled orbitals
of the ligands.
Octahedral, square planar and tetrahedral complexes are formed as a
result of d2sp3 or sp3d2 , dsp2 and sp3 hybridisation respectively.
 INNER ORBITAL COMPLEX

If the complex is formed by the use of inner d-orbitals for

hybridisation, it is called inner orbital complex.
Here, the electrons of the metal are forced to pair up.
Hence the complex will be either diamagnetic or will have lesser
number of unpaired electrons.
Such a complex is also called Low Spin Complex.
 OUTER ORBITAL COMPLEX

If the complex is formed by the use of outer d orbitals for

hybridisation, it is called an outer orbital complex.
This complex will have larger number of unpaired electrons.
Such a complex is also called High Spin Complex.
 APPLICATIONS OF
VALENCE BOND THEORY
 1. [Co(NH3)6]3+

Cobalt has the electronic configuration 4s23d7 .

In this complex, Co is in the +3 oxidation state.
The Co3+ ion is formed by the loss of two 4s and one 3d electrons.
Since NH3 is a strong ligand, the electrons in the 3d orbitals are forced

to pair up.
Since NH3 is a strong ligand, the electrons in the 3d orbitals are forced

to pair up.
The inner d orbitals are already vacant and these two 3d, one 4s and
three 4p orbitals hybridized to form six d2sp3 hybrid orbitals.
Six pairs of electrons, one from each NH3 molecule, occupy the six

vacant hybrid orbitals.

Thus the complex has octahedral geometry and is diamagnetic.
 2. [CoF6]3−

Cobalt has the electronic configuration 4s2 3d7.

In this complex, Co is in the +3 oxidation state.
The Co3+ ion is formed by the loss of two 4s and one 3d electrons.
Since Fluoride is a weak ligand, the electrons in the 3d orbitals are
not disturbed and the outer 4d orbitals are used for hybridization.
The six orbitals, one 4s, three 4p and two 4d orbitals hybridized to
form six sp3d2 hybrid orbitals.
Six pairs of electrons, one from each fluoride ions occupy the six
hybrid orbitals.
Thus the complex has octahedral geometry and is paramagnetic.
 3. [NiCl4]2−

Nickel has the electronic configuration 4s2 3d8 .

Nickel is in +2 oxidation state and the ion has the electronic
configuration 3d8 .
Since Chloride is a weak ligand, the electrons in the 3d orbitals are
not disturbed.
The four orbitals, one 4s, three 4p orbitals hybridized to form four sp3

hybrid orbitals.

Four pairs of electrons, one from each chloride ions occupy the four

hybrid orbitals.

Thus the complex has tetrahedral geometry and is paramagnetic.

 4. [NiCN4]2−

Nickel has the electronic configuration 4s2 3d8.

In this complex nickel is in +2 oxidation state.

The Ni2+ ion has the electronic configuration 3d8.

Since Cyanide is a strong ligand, the electrons in the 3d orbitals are

forced to pair up.

The four orbitals, one 3d, one 4s and two 4p orbitals hybridized to

form four dsp2 hybrid orbitals.

Four pairs of electrons, one from each cyanide ions occupy the four

hybrid orbitals.

Thus the complex has a square planar geometry and is diamagnetic.

 LIMITATIONS OF VALENCE BOND THEORY

It fails to explain the detailed magnetic properties.

It does not explain the colour exhibited by coordination compounds.

It does not give a quantitative interpretation of the thermodynamic

and kinetic stabilities of Coordination compounds.

It does not distinguish between weak and strong ligands.

CRYSTAL FIELD THEORY
 CRYSTAL FIELD SPLITTING IN OCTAHEDRAL COMPLEXES

In an isolated gaseous metal ion, the five d orbitals are degenerate.

In an octahedral complex six ligands approach the central metal ion
along the three Cartesian axes.
As the ligands approach, at first there is an increase in the energy of d
orbitals.
The orbitals lying along the cartesian axes, dx2−y2 and dz2 , get
repelled more strongly than the orbitals directed in between the
axes, dxy, dxz and dyz.
As a result, the energy of the dx2 −y2 and dz2 orbitals is increased and
the energy of dxy, dxz and dyz orbitals is decreased.
Thus the five d orbitals which were originally degenerate in the free
metal ion splits into two levels
(i) the doubly degenerate level called eg level which is of higher

energy and
(ii) the triply degenerate level called t2g level which is of lower

energy.
The splitting of the five d orbitals into eg and t2g energy levels by the

approaching ligands is called the crystal field splitting.

The energy difference between t2g and eg levels is called crystal field

splitting energy and is denoted as ∆o or 10Dq.

 CRYSTAL FIELD SPLITTING IN TETRAHEDRAL COMPLEXES

The tetrahedral arrangement of the four ligands around the central metal ion
is related to a cube.
The metal ion is at the centre of the cube.
Four of the eight corners of the cube are occupied by the ligands.
The dx2−y2 and dz2 orbitals (e orbitals) point along the x, y and z directions
(face centres).
The dxy, dxz and dyz orbitals (t2 orbitals) point in between x, y and z

directions (edge centres).

The direction of approach of ligands does not coincide exactly with either ‘e’
or ‘t2’ orbitals.

The dxy, dxz and dyz orbitals are pointing close to the direction in which
ligands are approaching.
As a result, the energy of these t2 orbitals increases much more than the

energy of the ‘e’ orbitals.

Thus the d orbitals split into two levels.
(i) the triply degenerate ‘t2’ orbitals of higher energy and

(ii) the doubly degenerate ‘e’ orbitals of lower energy.

 SPECTROCHEMICAL SERIES

It is a series in which the ligands are arranged in the increasing order

of magnitude of crystal field splitting.
 COLOUR IN COORDINATION COMPOUNDS

The crystal field splitting of d orbitals produces the energy difference ∆.

This energy difference is usually very small.
Thus promotion of electrons from lower to higher d level (d−d transition)
results from the absorption of light of higher wavelength in the visible region
and the complex appears coloured.
Depending on the wavelengths of light absorbed, the complex will have
different colours.
The d−d transition account for the colour of the complex ions and their
complexes.
MAGNETIC PROPERTIES
CALCULATION OF MAGNETIC MOMENT
 MERITS & LIMITATIONS OF CRYSTAL FIELD THEORY

The crystal field model is successful in explaining the formation, structures,

colour and magnetic properties of coordination compounds.
According to CFT, anionic ligands should exert the greatest splitting effect.
But actually the anionic ligands are found at the low end of the
Spectrochemical series.
CFT does not take into account the covalent character of bonding between
the ligand and the central metal atom.
 BONDING IN METAL CARBONYLS

Organometallic compounds in which CO acts as the ligand are called Metal

Carbonyls.

The organometallic compounds which contain only carbonyl ligands are

called homoleptic carbonyls.

Examples are Ni(CO)4 , Fe(CO)5 , Cr(CO)6 , Mn2(CO)10 etc.

The metal-carbon bond in metal carbonyls possess both s and p
character.
The M–C σ bond is formed by the donation of lone pair of electrons on
the carbonyl carbon into a vacant orbital of the metal.
The M–C π bond is formed by the donation of a pair of electrons from
a filled d orbital of metal into the vacant antibonding π* orbital of
carbon monoxide.
The metal to ligand bonding creates a synergic effect which
strengthens the bond between CO and the metal.
This type of bonding is called synergic bonding.
 STABILTY OF COORDINATION COMPOUNDS

The stability of a complex is a measure of the strength of the metal-ligand

bond.
Thus, stronger the metal ligand bond, the greater is the thermodynamic
stability of the complex.
The stability of a complex may also be defined as a measure of its resistance
to the replacement of one ligand by another.
 IMPORTANCE AND APPLICATIONS OF
COORDINATION COMPOUNDS

Hardness of water is estimated by simple titration with Na2EDTA.

The noble metals like gold and silver are extracted by the formation
of their cyano complexes.
Metals can be purified by the formation and subsequent
decomposition of coordination compounds.
Many medicines are complexes.

Complexes are used in electroplating.

Coordination compounds are used as catalysts for many industrial

processes.

Coordination compounds are of great importance in biological

systems like chlorophyll, haemoglobin, cyanocobalamine etc.