COORDINATION COMPLEX COMPUNDS

REVISE NOTES
Introduction
The Coordination compounds are very important in day to day life,
many compounds exist as coordination compounds as they have
special type of linkage that is coordinate bond .It is formed between
electron rich and electron deficient species.
Coordinate bond: It is a bond in which sharing of electrons occurs
but not mutual sharing. In this the shared pair is donated by only one
atom and the one that donates is donor and the other which accepts
is acceptor.
For example:
NH3: + BF3--à{H3N :-> BF3}
In this NH3 is donor atom as it has lone pair and BF3 is acceptor as it is
electron deficient compound.
The branch of chemistry that deals with the study of coordination
compounds are called as” coordinate chemistry “
Examples of some coordinate compounds like:
 Hemoglobin – coordination compound of iron (Fe)
 Chlorophyll – coordination compound of magnesium (Mg)
 Vitamin B12- coordination compound of cobalt (Co)
Most of time coordination compounds are confused with double
salts but there exists a lot difference between the two.
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Double salts
Double salt is the association of many substances or we can say they
mainly contain two salts in equimolar concentration.
1. like Mohr’s salt FeSO4.(NH4)2SO6H2O
2. Potash alum K2SOAl2 (SO4)3.24H2O etc.
In coordination compound once the compound is formed its ions
than the compound as a whole do not lose its identity but when
dissolved in water they show different properties whereas in case of
double salts they don’t show different properties but looses their
identity in water
{Co(NH3)6}Cl3à Co(NH3)6 + 3Cl (coordination compound in water )
FeSO4.(NH4)2SO4.6H2OàFe2+ ,NH4+,SO42-,H+,OH- ions (double salt in
water )
 Coordination compounds exist in solid as well as aqueous state
whereas the double salts exist in solid state and in aqueous
state they dissociate into ions .
 The coordination compounds exist in extended octet whereas
in double salts they exist in their own valances.
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Terminology involved
central metal atom:
 it is the acceptor metal atom present in the coordination
compound
 It is mostly d block element
 It act as an acceptor as it has vacant d orbital
 Due to accepting nature they act as Lewis acids
For example in complex: {Co(NH3)6}Cl3 in this Co is central metal
atom

Ligands:
 They are donor atom may be single atom or group of atoms
 They are negatively charged or neutral species with lone pair
Br-,Cl- etc or neutral like NH3,NO,CO etc
 They act as Lewis bases
 We can also call ligands as nucleophile as they are nucleus
loving
For example in complex: {Co(NH3)6}Cl3 in this NH3 is ligand

coordination sphere:
 It is the combination of atom and ligands.
Example: in [ Co (NH3)6 Cl3 ]
[ Co (NH3)6 ] is coordination entity or complex
 They are written in square brackets [coordination entity]
 This coordination sphere may be positively changed, negatively
charged
 If it is positively charged than it is called as cationic entity and
in case of negative charge it is anionic entity or complex.
Example: [Co(NH3)6]3+ cationic entity [Ag (CN)6]- anionic entity
counter ion:
  The atom or group of atoms written outside bracket is called
counter ion.
Example: in [Co(NH3)6].Cl3
Cl3 is a counter ion or the ionizable part when dissolved in water
 If coordination sphere is with positive charge than counter ion
is with negative charge or vice versa.
Coordination entity
 The central metal atom and ligands attached to it forms
coordination entity and is written within square brackets
Example :in [Co(NH3)6].Cl3
In this in [Co(NH3)6] is coordination entity
Nature of ligands: Their nature is determined by the property
denticity
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Denticity
it determines the total number of donor atoms in a molecule.
On the basis of the property denticity ligands are :
 Monodentate /unidentate: is that which has one donor atom
Examples : CN-, OH-,Cl-,Br-,NH3:,H2O,CO etc

 Di-dentate: if it has two donor atoms

Examples
(OXALATE ION)

(ethylene diamine )

 Polydentate : if it has 3 or more donor atoms in it DIETHYLENE

TRIAMINE (tridendate)
NH2-CH2-CH2-NH-CH2-CH2-NH2

Hexadentate: ethylene diamine tetra acetic acid (EDTA)

chelate: when the ligand has two or more donor atoms and they are
arranged in such a way that they give rise to a ring like structure than
the effect is called chelating and the ring formed is chelate .
For example:
uses of chelates:
 They are used in softening of hard water
 In qualitative analysis for detection of metal
 In separation of lanthanoids and actinoids

Ambidentate ligand: that have two donor atoms but doesn’t show
chelation. This group bond at a time by one atom.
For example: CN-,NO2 etc

Symmetrical and unsymmetrical ligands :

Symmetrical ligands: if ligands attached to central atom are of same
type
Example: ethylenediamine etc.

Unsymmetrical ligands: if ligands attached are of different type.

Example: glycinate ion etc.
Coordination number: it is the number of ligands bonded with the
central metal atom for example: IN [Ag (CN)2]-“the no. Of ligands
attached are 2 therefore coordination no. is 2 “.
Oxidation number: it is the residual chargeleft on the atom when all
other atoms are removed from it .it is calculated by assigning
appropriate charges to ligands and then equating the sum of the
charges on the central atom and the ligands equal to the charge on
the coordination sphere.
For example: [Co (NH3)6] Cl3 in this oxidation state of NH3 is 0 and for
Cl is -1, and ooxidation state of Co is taken as x then
(x-3) x 1=0 or x=+3
another example: [Cu (CN)4]3- in this oxidation state of Cu is
taken as x, CN as -1 so,
x + (-1 X 4) = -3 or x=+1

Homo-leptic and hetero-leptic compounds

Homoleptic: are those which have same kind of ligands attached to
central metal atom
Example:in [Co (NH3)6] Cl3 is homoleptic as ligands are same
terolyptic: when ligands attached are of different type
Example: in [CoCl3(NH3)3]3+ is heterolytic because ligands attached are
of different types.

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Denticity
it determines the total number of donor atoms in a molecule.
On the basis of the property denticity ligands are :
 Monodentate /unidentate: is that which has one donor atom
Examples : CN-, OH-,Cl-,Br-,NH3:,H2O,CO etc

 Di-dentate: if it has two donor atoms

Examples

(OXALATE ION)

(ethylene diamine )

 Polydentate : if it has 3 or more donor atoms in it DIETHYLENE

TRIAMINE (tridendate)
NH2-CH2-CH2-NH-CH2-CH2-NH2
Hexadentate: ethylene diamine tetra acetic acid (EDTA)

chelate: when the ligand has two or more donor atoms and they are
arranged in such a way that they give rise to a ring like structure than
the effect is called chelating and the ring formed is chelate .
For example:

uses of chelates:
 They are used in softening of hard water
 In qualitative analysis for detection of metal
 In separation of lanthanoids and actinoids

Ambidentate ligand: that have two donor atoms but doesn’t show
chelation. This group bond at a time by one atom.
For example: CN-,NO2 etc
Symmetrical and unsymmetrical ligands :
Symmetrical ligands: if ligands attached to central atom are of same
type
Example: ethylenediamine etc.

Unsymmetrical ligands: if ligands attached are of different type.

Example: glycinate ion etc.

Coordination number: it is the number of ligands bonded with the
central metal atom for example: IN [Ag (CN)2]-“the no. Of ligands
attached are 2 therefore coordination no. is 2 “.
Oxidation number: it is the residual chargeleft on the atom when all
other atoms are removed from it .it is calculated by assigning
appropriate charges to ligands and then equating the sum of the
charges on the central atom and the ligands equal to the charge on
the coordination sphere.
For example: [Co (NH3)6] Cl3 in this oxidation state of NH3 is 0 and for
Cl is -1, and ooxidation state of Co is taken as x then
 (x-3) x 1=0 or x=+3
another example: [Cu (CN)4]3- in this oxidation state of Cu is
taken as x, CN as -1 so,
x + (-1 X 4) = -3 or x=+1

Homo-leptic and hetero-leptic compounds

Homoleptic: are those which have same kind of ligands attached to
central metal atom
Example:in [Co (NH3)6] Cl3 is homoleptic as ligands are same
terolyptic: when ligands attached are of different type
Example: in [CoCl3(NH3)3]3+ is heterolytic because ligands attached are
of different types.
Nomenclature of coordination compounds
Like for ionic compounds the naming is done by writing first cation
name and then naming anion.
For example: NaCl is ionic and written as sodium chloride that is in
name first part is cationic and other is anionic.
In the same way coordination compounds consist of two parts:Cation
and anion. While naming,the name of cationic part is written first
followed by anionic part. There are certain set of rules that are
followed while writing name of cation.

Naming for cationic species: in which coordination sphere is

positively charged
 Name of cation is written first
Let’s say the coordination sphere is cationic that is with positive
charge for example [Co (NH3)6] Cl3 for the naming of coordination
entity is done first and later the counter ion .so in given complex the
name of [Co (NH3)6] is written first than the counter ion Cl
 In case of coordination entity: the name of ligands is written
first and then the central metal atom. Forexample, in this [Co
(NH3)6]the name of NH3 is written first than for Co.
 If the ligands are homoleptic than you can write in any manner
but if they are heterodetic than the alphabetical order is
followed
For example: in complex [Co (NH3)5CL] the name of ligands is written
in alphabetical order that is for ammine firstand then chloro.
Rules for writing the name of the ligand:
 If the ligand names end with ‘ate’ or ‘its‘than e is replaced by o
Like for oxalate it is written as oxalate, sulphite as sulphito
 If ligand name end with’ ide ‘than ide is replaced by ‘o ‘
Example for chloride it becomes chlorido
 Neutral ligands are name as such like for water it is aqua, for
ammonia it is ammine
 If more than one ligand is present than alphabetical order is
followed and di,tri, tetra is prefixed before the name of ligand.
For example: in complex [Co (NH3)6] ligand name will be hexamine
that is hexa for 6
 For polydentate ligands they include numerical prefix –like di is
replaced by bi, tri is replaced by tris, tetra is replaced bytetra is
so on
For example: [CoCl2(en)2] Cl in this the ligands are
dichlorobisethylenediamine
In case of Central metal atom:
Oxidation state of central metal atom is written in numeral after the
name of central metal atom
For example: in complex [Co (NH3)6] Cl3 it is hexamine cobalt (III) that
is cobalt (III) is central metal atom with its Oxidation state in numeral
 if complex is cationic than normally the name is used: example
is same as given above
 if complex is anionic than metal atom name ends with ate
for example: in complex K3[fe(CN)6] in this the name is written as
potassium hexacyanoferrate(III) that is in this example coordination
entity is anionic complex and the name of central metal atom is
written with ate followed by Oxidation state in numeral
 if complex is neutral than the normal central metal atom name
is used
some commonly used ligands:
 bromo Br-
 floro F-
 oxo
 hydroxo OH-
 cyano CN-
 carbonato CO32-
 acetate CH3COO-
 ammine NH3
 aqua H2O
 nitrosyl NO
 carbonyl CO
 dioxygen O2
  dinitrogen N2
 pyridine C5H5N
 ethylene diamine H2NCH2CH2NH2
some examples of iupac naming:
1. [Cr (NH3)(H2O)3]Cl3
Triaminetriaquachromium(III)chloride
2. [Co(en)3]2(SO4)3
Trisethylenediaminecobalt(III)sulphate
3. [Ag(NH3)2][Ag(CN)2]
Diamine argentum(i)dicyanoargentate(i)
4. [Pt (NH3)2Cl (NO2)]
Diaminechloronitroplatinum(III)
5. K3[Cr(C2O4)3]
Potassiumtrioxalatochromate(III)
Isomerism in Coordination Compounds
Isomerism is the phenomenon in which compounds have same
molecular formula but different structures and these different
structures are called as isomers. Isomers are those that have different
physical and chemical properties.
There are two types of isomers:
 Structural isomerism
 Stereoisomerism
Structural isomerism: Different types are as follows:-
 ionization isomerism
 Hydrate isomerism
  Coordination isomerism
 Linkage isomerism
Stereoisomerism: Different types are as follows:-
 geometrical isomerism
 Optical isomerism
Structural isomerism:The compounds have same molecular
phenomenon but different structures
 Ionization isomerism: they differ in productions of ions in
aqueous solution
For example:à [CoBr(NH3)5]SO4 and [Co (NH3)5SO4 ]Br are
ionization isomers when dissolved in water
[CoBr(NH3)5]SO4 à[CoBr(NH3)5]2+ + SO42-
[Co (NH3)5SO4 ]Bràà[CoSO4 (NH3)5]2+ + Br-
 Hydrate or solvate isomerism: in this they differ in number of
molecules of water of crystallization
For example: [Cr(H2O)6]Cl3 and [Cr(H2O)5Cl]Cl2H2Oare hydrate isomers
When dissolved in water
[Cr(H2O)6]Cl3à[Cr(H2O)6] + 3Cl- (no water molecule )
[Cr(H2O)5Cl]Cl2H2Oà[Cr(H2O)5Cl]+2Cl+H2O(will give one water
molecule )

 Coordination isomerism: they differ in coordination entities

For example:[Co(NH3)6] [Cr(CN)6] and :[Co(CN)6] [Cr(NH3)6] are
coordination isomers
 Linkage isomerism: it is in case of ambidentate ligands and in
this they differ in the point of attachment.
For example, in case of CN(cyano) and in case of NC (isocyano)
 Stereoisomerism: in these compounds have same molecular
formula but differ in spatial arrangements of ligands.
It is of two types:
 Geometrical isomerism
 Optical isomerism
Geometrical isomerism: it is due to difference in the geometrical
arrangements of ligands around central metal atom.
it is of further two types :
 Cis
 Trans
Cis : when the similar ligands are on adjacent position
Trans : when the similar ligands are on opposite positions
Cis and trans isomers are shown below (this is shown by compounds
with coordination number 4 and 6
Example: [Pt (NH3)4Cl2]
  Another type of Geometrical isomerism that occurs in
octahedral compounds in Ma3b3 like [Co(NH3)3(NO3)3].
It can be of two types :
 Facial
 Meridional

Fac :In this three donor atoms of same ligands occupy adjacent
positions at corners of an octahedral face
mer :In this three donor atoms of same ligands occupy positions
around the meridian of an octahedron.

 Optical isomers:they can also show optical isomerism if chiral

center is present in them .if they possess chiral center they can
rotate the plane of polarized light .
Example: [Co(en)3]
Bonding in coordination compounds
The first theory in order to explain it was given by Alfred Werner in
1892.
He performed various experiments to show that the surrounding
atoms exist around central atom. He actually conducted ppt. studies
CoCl2+NH3àCoCl3.6NH3
When CoCl3.6NH3 was precipitated with AgNO3 it gave 3 moles of
AgCl this shows that 3 Chloride ions are not directly bonded with
cobalt that is why it was precipitated with silver nitrate which gave
him the idea about primary and secondary valances’ and accordingly
he postulated his theory.
Werner’s theory
According to the theory the postulates are:
1. Metal exhibit 2 types of vacancies: primary valency and
secondary valency
2. Primary valency gives the information about oxidation state and
secondary valency gives the information about coordination
number
3. Primary valency is variable whereas secondary valency is always
fixed
4. Secondary valency that is coordination number determines the
geometry of molecule or we can say polyhedral of the
molecule.
5. Metal stabilize all its vacancies
Depending upon this theory various structures of coordination
compound was explained :
In CoCl3. (NH3)6 à In this NH3 is secondary valency and Cl is primary
valency
In CoCl3.(NH3)5 the ionizable chlorides are only 2

In COCl3.(NH3)4 the ionizable ions are only one chloride ion

Please note the dark lines shows ionizable part and light lines show
non ionizable part in all the figures.
Limitations of Werner’s theory:
He was able to explain many facts about coordination compounds
but failed to give any information about why only certain elements
participate in coordinate bond, why the coordination entity has
special geometry …
Due to these reasons other theory was proposed that is valence bond
theory
Valence bond theory
It was given by Pauling in 1931
 1. He proposed the idea of donating lone pair to central metal
atom.
2. Bonding in coordination compound occur due to overlap of
orbital of ligand with vacant orbital of central metal atom
3. All the vacant d orbitals have same energy. but the degeneracy
of d orbital breaks when ligand approaches
4. Hybridization is considered while drawing polyhedral
5. Metal ions in presence of ligands can use their (n-1)d ns np or
ns np Nd.
If the inner d orbital is used than the complex is regarded as inner
orbital complex and if outer d orbital is used than the complex is
outer orbital complex.
6. The ligands decide which orbitals out of these to be used and
accordingly the geometry is decided.
If hybridization
 sp3- tetrahedral
 dsp2-square planar
 Sp3d-trigonal bipyramidal
 Sp3d2- octahedral
 d2sp3-octahedral
For example:
For any coordination compound: To find the shape using valence
bond theory following steps to be followed
1. Remove the electrons from the metal and form it the ion
2. Rearrange metal electrons if necessary
3. Hybridization
 4. Overlapping of hybrid orbitals of metal with ligand
Let us take one example: of example [Co(NH3)6]3+. In this central
metal atom Co atomic no. is 27. The electronic configuration of Co =
(Ar)183d74s2
Co3+=(Ar)183d6

Example [Fe(Co)5]: (inner orbital complex and diamagnetic )

EXAMPLE: in [CoF6]3-…… (outer orbital complex and paramagnetic )

Drawbacks of valence bond theory:

1. This theory couldn’t have valid reason behind that why some
complexes of metal oxidation state is inner orbital while in
 some other complexes the same metal atom ion in same state
form outer orbital complex.
2. The magnetic behavior explained wasn’t satisfactory
3. This theory couldn’t give the information about color of
compounds
4. This theory failed to distinguish between strong and weak
ligand
TO OVERCOME THE SHORT COMINGS A NEW THEORY WAS
PROPOSED: CRYSTAL FIELD THEORY
Crystal field splitting theory
It was given by Hans Bethe Ans John van vleck
Postulates
1. It assumes the central metal atom and ligands as point charges
2. When a complex is formed: central metal atom positive charge
Ligands –have negative charge
3. This theory considers the interaction between central metal
atom and ligand is purely electrostatic
4. When a complex is formed the central metal atom is
surrounded by oppositely charged ligands
5. No hybridization takes place
6. To form a bond the ligand molecule must approach towards
central metal atom
7. In absence of external magnetic field, the d orbital of central
metal atom is degenerate but this degeneracy breaks when
ligand approaches.
8. The d orbital splits into two sets:
Axial set non-axial set
dxy,dyz, dzx dx2-y2,dz2

This is crystal field splitting.

9. Repulsive forces occur between electrons of metal and with
lone pair ligands due to which energy of electron fluctuate or
changes.
For octahedral complexes
To form octahedral complex the ligands, have to approach central
metal atom along the coordination axis. During the approach the d
orbitals whose lobes lie along the axis will experience more repulsion
due to this their energy will increase and the other non axial set will
suffer less repulsion. as a result, the non-axial will have less energy as
compare to axial set (eg greater than t2g)

Tetrahedral complex:
The ligands have to approach central metal atom in between the
coordinationaxis. during the approach the d orbital’s whose lobes lie
along the axis will experience less repulsion due to this their energy
will increase and the other non axial set will suffer more repulsion. as
a result, the non-axial will have more energy as compared to axial set
(t2g greater than eg )

square planar complex:

In the different order is seen i.e
dx2-y2,dxy,dz2,dyz,dzx

Please note for all the complexes:

for strong ligands : the CFSE is more therefore pairing will occur
for weak ligands : the CFSE Is less
Organo-metallic compounds
They are those compounds in which metal or metalloid or a non-
metal is directly linked to carbon atom of a hydrocarbon.
For example: (C2H5)2Zn etc
Please note that metal cyanides and metal carbides are not
organometallic compounds as in them carbon atom is not directly
joined to metal.
Types of organometallic compounds:
 Sigma organometallic compounds
 Pi organometallic compounds
Sigma and pi organometallic compounds In detail:
 Sigma organo-metallic compounds: these are the compounds
obtained by bonding of non-metal with metalloid elements
with carbon. forexample:RMgX, (CH3)3Al etc.
 Pi organo- metalliccompound: these compounds are formed
mainly by transition elements. Normal sigma bond is formed
through the pi electron cloud of organic molecule. Forexample :
ferrocene ,zeisse’s salt etc
 Sigma and pi organo-metaliccompound: these compounds are
formed by transition metal carbonyls .for example :
Ni(CO)4,Fe(CO)5 etc
Shapes of these structures are shown below:
For example :
1. Shape of [Ni(Co)4]

Shape of [Fe(Co)5]
Considering bonding in metal carbonyls: these compounds possess
both s and p characters. The M-C sigma bond is formed by donation
of lone pair if electrons on the carbonyl carbon into a vacant orbital
of metal. The M-C pi bond is formed by the donation of pair of
electrons from the filled d orbital of metal into vacant antibonding pi
orbital of carbon monoxide. The metal to ligand bonding creates a
synergic effect which strengthens the bond between CO and metal as
shown below:-

Applications of coordination compounds

1. They are used in estimation of hardness of water as calcium
and, magnesium ions form complexes with EDTA.
2. It is used in estimation and detection of metal ions. for
example: Ni2+ions is estimated using dimethyl glyoxime
3. It is used in Extraction of metals
4. It is used in medicines like cis platin is used in treatment of
cancer
5. It is used in animal and in plant world like hemoglobin is a
complex of iron, chlorophyll is a complex of magnesium and so
on