Chapter 5
Co ordination compound
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:
• Haemoglobin – 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.
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.
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
(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 haemoglobin is a complex of
iron, chlorophyll is a complex of magnesium and so on