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.

Double salts

Double salt is the association of many substances or we can say they

mainly contain two salts in equimolar concentration.

like Mohr’s salt FeSO4.(NH4)2SO6H2O

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.
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

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

Class_12_Coordination_Compounds_Oxalate_Ion

(OXALATE ION)

Class_12_Coordination_Compounds_Ethylene_Diamine_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)

Class_12_Coordination_Compounds_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:

Class_12_Coordination_Compounds_Chelate

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.

Class_12_Coordination_Compounds_Symmetrical_Ligands

Unsymmetrical ligands: if ligands attached are of different type.

Class_12_Coordination_Compounds_Glycinate_Ion

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:

[Cr (NH3)(H2O)3]Cl3
Triaminetriaquachromium(III)chloride

[Co(en)3]2(SO4)3
Trisethylenediaminecobalt(III)sulphate

[Ag(NH3)2][Ag(CN)2]
Diamine argentum(i)dicyanoargentate(i)

[Pt (NH3)2Cl (NO2)]

Diaminechloronitroplatinum(III)

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]

Class_12_Coordination_Cis_Isomerism

Class_12_Coordination_Trans_Isomerism

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]

Class_12_Coordination_Optical_Isomerism

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:

Metal exhibit 2 types of vacancies: primary valency and secondary valency

Primary valency gives the information about oxidation state and secondary
valency gives the information about coordination number
Primary valency is variable whereas secondary valency is always fixed
Secondary valency that is coordination number determines the geometry of
molecule or we can say polyhedral of the molecule.
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

Class_12_Coordination_Compounds_Different_Structures

In CoCl3.(NH3)5 the ionizable chlorides are only 2

Class_12_Coordination_Compounds_Different_Structures_1

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

Class_12_Coordination_Compounds_Different_Structures_2

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

He proposed the idea of donating lone pair to central metal atom.

Bonding in coordination compound occur due to overlap of orbital of
ligand with vacant orbital of central metal atom
All the vacant d orbitals have same energy. but the degeneracy of d
orbital breaks when ligand approaches
Hybridization is considered while drawing polyhedral
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.

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

Remove the electrons from the metal and form it the ion
Rearrange metal electrons if necessary
Hybridization
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

Class_12_Coordination_Compounds_Structure_1

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

Class_12_Coordination_Compounds_Structure_3

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

Class_12_Coordination_Compounds_Structure_2

Drawbacks of valence bond theory:

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.
The magnetic behavior explained wasn’t satisfactory
This theory couldn’t give the information about color of compounds
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

It assumes the central metal atom and ligands as point charges

When a complex is formed: central metal atom positive charge
Ligands –have negative charge

This theory considers the interaction between central metal atom and
ligand is purely electrostatic
When a complex is formed the central metal atom is surrounded by
oppositely charged ligands
No hybridization takes place
To form a bond the ligand molecule must approach towards central metal
atom
In absence of external magnetic field, the d orbital of central metal
atom is degenerate but this degeneracy breaks when ligand approaches.
The d orbital splits into two sets:
Axial set non-axial set

dxy,dyz, dzx dx2-y2,dz2

Class_12_Coordination_Compounds_d_Orbitals

This is crystal field splitting.

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)

Class_12_Coordination_Octahedral_Complex

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 )

Class_12_Coordination_Tetrahedral_Complex
square planar complex:

In the different order is seen i.e

dx2-y2,dxy,dz2,dyz,dzx

Class_12_Coordination_Square_Planar_Complex

Please note for all the complexes:

for strong ligands : the CFSE is more therefore pairing will occur

for weak ligands : the CFSE Is less

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:

Metal exhibit 2 types of vacancies: primary valency and secondary valency

Primary valency gives the information about oxidation state and secondary
valency gives the information about coordination number
Primary valency is variable whereas secondary valency is always fixed
Secondary valency that is coordination number determines the geometry of
molecule or we can say polyhedral of the molecule.
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

Class_12_Coordination_Compounds_Different_Structures

In CoCl3.(NH3)5 the ionizable chlorides are only 2

Class_12_Coordination_Compounds_Different_Structures_1

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

Class_12_Coordination_Compounds_Different_Structures_2

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

He proposed the idea of donating lone pair to central metal atom.

Bonding in coordination compound occur due to overlap of orbital of
ligand with vacant orbital of central metal atom
All the vacant d orbitals have same energy. but the degeneracy of d
orbital breaks when ligand approaches
Hybridization is considered while drawing polyhedral
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.

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

Remove the electrons from the metal and form it the ion
Rearrange metal electrons if necessary
Hybridization
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

Class_12_Coordination_Compounds_Structure_1
Example [Fe(Co)5]: (inner orbital complex and diamagnetic )

Class_12_Coordination_Compounds_Structure_3

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

Class_12_Coordination_Compounds_Structure_2

Drawbacks of valence bond theory:

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.
The magnetic behavior explained wasn’t satisfactory
This theory couldn’t give the information about color of compounds
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

It assumes the central metal atom and ligands as point charges

When a complex is formed: central metal atom positive charge
Ligands –have negative charge

This theory considers the interaction between central metal atom and
ligand is purely electrostatic
When a complex is formed the central metal atom is surrounded by
oppositely charged ligands
No hybridization takes place
To form a bond the ligand molecule must approach towards central metal
atom
In absence of external magnetic field, the d orbital of central metal
atom is degenerate but this degeneracy breaks when ligand approaches.
The d orbital splits into two sets:
Axial set non-axial set

dxy,dyz, dzx dx2-y2,dz2

Class_12_Coordination_Compounds_d_Orbitals

This is crystal field splitting.

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)

Class_12_Coordination_Octahedral_Complex

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 )

Class_12_Coordination_Tetrahedral_Complex

square planar complex:

In the different order is seen i.e

dx2-y2,dxy,dz2,dyz,dzx

Class_12_Coordination_Square_Planar_Complex

Please note for all the complexes:

for strong ligands : the CFSE is more therefore pairing will occur

for weak ligands : the CFSE Is less

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:

Metal exhibit 2 types of vacancies: primary valency and secondary valency

Primary valency gives the information about oxidation state and secondary
valency gives the information about coordination number
Primary valency is variable whereas secondary valency is always fixed
Secondary valency that is coordination number determines the geometry of
molecule or we can say polyhedral of the molecule.
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

Class_12_Coordination_Compounds_Different_Structures

In CoCl3.(NH3)5 the ionizable chlorides are only 2

Class_12_Coordination_Compounds_Different_Structures_1

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

Class_12_Coordination_Compounds_Different_Structures_2

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

He proposed the idea of donating lone pair to central metal atom.

Bonding in coordination compound occur due to overlap of orbital of
ligand with vacant orbital of central metal atom
All the vacant d orbitals have same energy. but the degeneracy of d
orbital breaks when ligand approaches
Hybridization is considered while drawing polyhedral
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.
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

Remove the electrons from the metal and form it the ion
Rearrange metal electrons if necessary
Hybridization
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

Class_12_Coordination_Compounds_Structure_1

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

Class_12_Coordination_Compounds_Structure_3

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

Class_12_Coordination_Compounds_Structure_2

Drawbacks of valence bond theory:

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.
The magnetic behavior explained wasn’t satisfactory
This theory couldn’t give the information about color of compounds
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

It assumes the central metal atom and ligands as point charges

When a complex is formed: central metal atom positive charge
Ligands –have negative charge

This theory considers the interaction between central metal atom and
ligand is purely electrostatic
When a complex is formed the central metal atom is surrounded by
oppositely charged ligands
No hybridization takes place
To form a bond the ligand molecule must approach towards central metal
atom
In absence of external magnetic field, the d orbital of central metal
atom is degenerate but this degeneracy breaks when ligand approaches.
The d orbital splits into two sets:
Axial set non-axial set

dxy,dyz, dzx dx2-y2,dz2

Class_12_Coordination_Compounds_d_Orbitals

This is crystal field splitting.

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)

Class_12_Coordination_Octahedral_Complex

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 )

Class_12_Coordination_Tetrahedral_Complex

square planar complex:

In the different order is seen i.e

dx2-y2,dxy,dz2,dyz,dzx
Class_12_Coordination_Square_Planar_Complex

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 :

Shape of [Ni(Co)4]

Class_12_Coordination_Compounds_Shape1_Of_Organo_Metallic_Compounds

Shape of [Fe(Co)5]

Class_12_Coordination_Compounds_Shape2_Of_Organo_Metallic_Compounds

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:-

Class_12_Coordination_Compounds_Bonds
Applications of coordination compounds

They are used in estimation of hardness of water as calcium and,

magnesium ions form complexes with EDTA.
It is used in estimation and detection of metal ions. for example:
Ni2+ions is estimated using dimethyl glyoxime
It is used in Extraction of metals
It is used in medicines like cis platin is used in treatment of cancer
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