“ ज्ञान, विज्ञान आवि सु संस्कार यांसाठी विक्षिप्रसार ”

- विक्षिमहर्षी डॉ. बापू जी साळुं खे.

श्री स्वामी वििेकानं द विक्षण संस्था, कोल्हापूर.

विद्या सवमवि
E- Content Development
Shri Swami Vivekanand Shikshan Sanstha
Kolhapur
Shri Swami Vivekanand Shikshan Sanstha
Kolhapur
 9. Co-ordination Compounds
Combination of two or more stable compounds in stoichiometric ratio give
two substances namely double salt and coordination complexes.
Double salts: Addition compounds which exist in solid state but dissociate
into their ions when dissolved in water are called double salt. A double salt
dissociates in water into simple ions.
Example- K2SO4.Al2(SO4)3.24H2O
Potash alum

FeSO4.(NH4)2SO4.6H2O Water Fe2+ (aq) + 2 NH4+ (aq) + 2 SO42- (aq)

Mohrs salt
Water
KCl.MgCl2.6H2O K+(aq) + Mg 2+ (aq) + 3Cl - (aq)
Carnalite

Shri Swami Vivekanand Shikshan Sanstha

Kolhapur
Co-ordination Complex: Addition compounds which retain their identity in
aqueous solution are called Co-ordination Complexes. They show different
properties from their ions. A coordination complex dissociates in water with at least
one complex ion. They contain co-ordinate bonds.
A coordinate bond is represented by an arrow
K4[Fe(CN)6] Water 4 K+ (aq) + [ Fe(CN)6] 4-
Potassium ferrocyanide Counter ion Complex ion
Structure of co-ordination complex K4[Fe(CN)6]

CN
CN CN
K4 Fe
CN CN
CN

Counter ion Complex ion

Shri Swami Vivekanand Shikshan Sanstha
Kolhapur
Transition metal ions form stable complex ions because-
i. they have multiple oxidation states.
ii. they have large charge to radius ratio.
iii. they have vacant low energy orbitals to accommodate the
electrons donated by the ligand.
Example- K4[Fe(CN)6]
Potassium ferrocyanide

Shri Swami Vivekanand Shikshan Sanstha

Kolhapur
Terms used in co-ordination compounds:
i. Complex: A central metal atom or ion which is surrounded by a
cluster of ions or molecules is called complex.
If the complex is an ion, it is called complex ion and if it is a
neutral species, it is called co-ordination compound or complex.
ii. Central atom or central ion or center of co-ordination:
In complex ion the metal atom or cation is attached to number
of ions or groups through co-ordinate bond is known as central
metal atom or ion.
Example- [ Ni(NH3)6 ]2+ Central metal ion: Ni2+
Central metal ion act as Lewis acid by accepting electron pairs
Shri Swami Vivekanand Shikshan Sanstha
donated by ligands. Kolhapur
iii. Ligand: The molecule or ion which is linked to central metal atom or ion
through co-ordinate bonds is called ligand. It acts as Lewis base by donating
lone pair of electron present on its donor atom.
Example- [ Ni(NH3)6 ]2+ Central metal ion: Ni2+ Ligand: NH3
iv. Co-ordination number: The number of ligand donor atoms which are directly
bonded to central metal atom by co-ordinate bonds is called co-ordination
number.
Example- [Ag(CN)2] - : C. N. = 2 [Cu(NH3)4] 2+ : C. N. = 4
[Cr(H2O)6]3+ : C. N. = 6 K4[Fe(CN)6] : C. N. =6
[ Fe(C2O4)3]3- : C. N.= 6 [because C2O4 2- is bidentate ligand ]
[Co(en)3]3+ : C. N.= 6 [ because en is bidentate ligand ]
v. Co-ordination sphere: The central metal atom or ion and the ligands attached to
it are written inside the square bracket and is called co-ordination sphere.
Example- [ Ni(NH3)6 ]2+ Shri Swami Vivekanand Shikshan Sanstha
Kolhapur
vi. Counter ions: The ionisable groups outside the square bracket
are called counter ions.
In K3 [Fe(CN)6] the co-ordination sphere is [Fe(CN)6]3- and the
counter ion is 3K+
CN
CN CN
K3 Fe
CN CN
CN
Shri Swami Vivekanand Shikshan Sanstha
Kolhapur
Co-ordination polyhedron: It is the spatial arrangement of
ligands about the central metal atom.
Example- tetrahedral, square planar, octahedral etc.
L L
L L L L
M M M
L L L L
L L L
L

Tetrahedral Square planar Octahedral

Shri Swami Vivekanand Shikshan Sanstha
Kolhapur
Classification of ligands on the basis of charge:
1. Negative ligands: CN- , Br -, NH2-
2. Neutral ligands: H2O , NH3
Classification of ligands on the basis of number of donor sites:
1. Monodentate or unidentate: They have only one donor atom.
Example- H2O , CN-
2.Bidentate: They have two donor atoms.
Example-
CH2 - NH2 COO- Or [C2O4]2- Or O=C-O-
CH2 - NH2 , COO- O=C-O-
Ethylene diamine Oxalate ion
Shri Swami Vivekanand Shikshan Sanstha
Kolhapur
3.Polydentate: They have two or more more donor atoms.
Example- Hexadentate ligand
EDTA [Ethylene diamine tetraacetate]
-OOC-CH CH2-COO-
2
N-CH2-CH2-N
-OOC-CH CH2-COO-
2

Denticity: The number of atoms in a single ligand that bind to a central atom
in a co-ordination compound is called denticity.
Shri Swami Vivekanand Shikshan Sanstha
Kolhapur
Classification of ligands on the basis of bonding:
1. Chelating ligands: A polydentate ligand which forms more than one co-ordinate
bond in such a way that a ring is formed is called chelating ligand.
Example- CH2 - NH2
CH2 - NH2

2. Ambidentate ligands: Monodentate ligands which contains more than one co-
ordinating atom are called ambidentate ligands.

Example- CN- has two donor atoms ( C and N ) and forms M-CN or M-NC bonds.

NO2- has two donor atoms ( N and O ) and forms M- NO2 or M-ONO bonds.

Shri Swami Vivekanand Shikshan Sanstha

Kolhapur
Oxidation number of central metal atom: If all the ligands are
removed along with electron pairs shared with metal atom then
the charge on metal atom is called oxidation number. It is
represented by Roman numeral such as Fe(III).
a) Calculation of oxidation number of Cu in [Cu(NH3)4]SO4 :
Suppose O.N. of Cu is x , then
x + 4(0) – 2 = 0
x = +2
b) Calculation of oxidation number of Fe in [Fe(CN)6]3- :
Suppose O.N. of Fe is x , then
x + 6(-1) = -3
x = +3

Shri Swami Vivekanand Shikshan Sanstha

Kolhapur
Charge number of a complex ion: The net charge
carried by complex ion is called its charge number.
Charge number of [Fe(CN)6]4 -
= Charge on Fe2+ + 6 x charge on CN- ion
= +2 +6 (-1)
= -4

Shri Swami Vivekanand Shikshan Sanstha

Kolhapur
Postulates of Werner’s co-ordination theory:
1) Central metal atom in a complex has two types of valencies .
(i) Primary valency and (ii) secondary valency
2) Primary valency is ionisable and secondary valency is non- ionisable.
3) Primary valency corresponds to oxidation state and secondary valency
corresponds to co-ordination number of the metal.
4) Primary valencies are satisfied by negative ions while secondary valencies are
satisfied by negative ions or neutral molecules.
5) Primary valencies are non-rigid and non-directional.
6) Every element have a fixed number of secondary valencies. The secondary
valencies are directed towards fixed position in spaces. Secondary valency
leads to geometry of complex.

Shri Swami Vivekanand Shikshan Sanstha

Kolhapur
Structure of co-ordination complex [Co(NH3)6]Cl3

NH3
NH3 NH3
Co Cl3
NH3 NH3
NH3
Coordination (secondary) sphere Ionization (primary) sphere
Shri Swami Vivekanand Shikshan Sanstha
Kolhapur
Classification of complexes on the basis of type of ligands-
i] Homoleptic complexes: Complexes in which all ligands are of only one kind are
called homoleptic complexes. Example - [CO(NH3)6]3+
ii] Heteroleptic complexes: Complexes in which ligands are of more than one kind
are called heteroleptic complexes. Example - [CO(NH3)4Cl2]3+
Classification of complexes on the basis of charge on complex-
i] Cationic complexes: Complexes in which complex ion carries positive charge are
called cationic complexes.
[CO(NH3)6] Cl3 [CO(NH3)6] 3+ + 3Cl-
ii]Anionic complexes: Complexes in which complex ion carries negative charge are
called anionic complexes.
K4[Fe(CN)6] 4 K+ + [Fe(CN)6] 4-
iii]Neutral complexes: Complexes which carry no charge are called neutral
complexes.
e.g. [Ni(CO)4], [Pt(NH3)2Cl2]
Shri Swami Vivekanand Shikshan Sanstha
Kolhapur
Effective atomic number: It is total number of electrons
around the central metal ion present in a complex and
is calculated as follows-
EAN = Z – X + Y
Z = Atomic number of metal.
X = Number of electrons lost during the formation of metal ion
from its atom.
Y = Number of electrons donated by the ligands.

Shri Swami Vivekanand Shikshan Sanstha

Kolhapur
For example- 1] In ferrocyanide ion [Fe(CN)6]4- 2] In [Co(NH3)6]3+
Z = 26, X =2 , Y= 6 x 2e- = 12 Z = 27, X =3 , Y= 6 x 2e- = 12
EAN = Z – X + Y EAN = Z – X + Y
EAN = 26 – 2 + 12 = 36 EAN = 27 – 3+ 12 = 36

3] In ferricyanide ion [Fe(CN)6]3-

Z = 26, X =3 , Y= 6 x 2e- = 12
EAN = Z – X + Y
EAN = 26 – 3 + 12 = 35
This compound do not obey EAN rule
EAN rule: A metal ion accept electron pairs from the ligands till the total number
of electrons present around the metal ion in the complex becomes equal to the
atomic number of the next rare gas atom.
If EAN is equal to 18(Ar), 36(Kr), 54(Xe), or 86(Rn) then the EAN rule is obeyed.

Shri Swami Vivekanand Shikshan Sanstha

Kolhapur
IUPAC names of anionic ligands-
Anionic ligand IUPAC name Anionic ligand IUPAC name
F- Fluoride Fluro OH- Hydroxide Hydroxo
Cl- Chloride Chloro C2O4 2- Oxalate Oxalato

Br- Bromide Bromo

NO2- Nitrite Nitro [ For
N- bonded ligand ]
I- Iodide Iodo
ONO- Nitrite Nitrito [ For
CN- Cyanide Cyano O- bonded ligand ]
SO4- Sulphate Sulphato SCN- Thiocynate Thiocyanato[ For
NO3- Nitrate Nitrato S- bonded ligand ]
CO3 2- Carbonate Carbonato NCS- Thiocynate Isothiocynato [ For
N- bonded ligand ]
Shri Swami Vivekanand Shikshan Sanstha
Kolhapur
IUPAC names of neutral ligands-

Neutral ligand IUPAC name

NH3 , Ammonia Ammine
[ Note spelling ]
CO, Carbon monoxide Carbonyl

H2O, Water Aqua

en, Ethylene diamine Ethylene diamine

Ethane-1,2-diamine
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Kolhapur
IUPAC names of metals in anionic complexes

Metal IUPAC name Metal IUPAC name

Aluminium [Al] Aluminate Chromium [Cr] Chromate

Cobalt [Co] Cobaltate Copper [Cu] Cuprate
Gold [Au] Aurate Iron [Fe] Ferrate
Manganese [Mn] Manganate Nickel [Ni] Nickelate
Platinum Platinate
Zinc [Zn] Zincate
Shri Swami Vivekanand Shikshan Sanstha
Kolhapur
IUPAC Nomenclature of co-ordination compounds:
Rules: 1) The cation is named first and then anion.
2) A complex cation is named by naming the ligands and then the
metal ion. After this the oxidation state of the
metal is written in roman number within the bracket.
Ligands metal (oxidation state)

3) A complex anion is named by writing ligands followed by the

name of the metal ending with suffix –ate.
For example- ferrate, cobaltate etc.

Shri Swami Vivekanand Shikshan Sanstha

Kolhapur
4) A non-ionic complex is named as one word. There
is no space between name of ligand metal cation
and counter ion.
5) The ligands are written in alphabetical order
irrespective of charge.
6) Two or more identical ligands are named using
prefixes like di, tri, tetra, penta, etc.
7) Number of polydentate ligands are indicated by using
prefixes like bis, tris ,tetrakis etc.
Shri Swami Vivekanand Shikshan Sanstha
Kolhapur
IUPAC names of complex cations-
[Cu(NH3)4]2+ Tetraamminecopper(II)ion
[Fe(H2O)5(NCS)]2+ Pentaaquaisothiocyanatoiron(III)ion
[Pt(en)2(SCN)2]2+ Bis(ethylenediamine)dithiocyanatoplatinum(IV)ion
3+
[Cr(NH3)6] Hexamminechromium(III) ion
3+
[Cr(H2O)6] Hexaaquachromium(III) ion
3+
[Co(en)3] Tris(ethane 1,2-diammine)cobalt(III) ion
IUPAC names of complex anions-
[Ni(CN)4]2- Tetracyanonickelate(II)ion
[Co(C2O4)3]3- Trioxalatocobaltate(III)ion
[Fe(CN)6]4- Hexacyanoferrate(II)ion
Shri Swami Vivekanand Shikshan Sanstha
Kolhapur
 3-
[Cr(CN)6] Hexacyanochromate(III) ion
2-
[NiCl4 ] Tetrachloronickelate(II) ion
2-
[Cd(SCN)4] Tetrathiocyanato-S-cadmiate(II) ion
IUPAC names of compounds containing complex cations -
[PtBr2(NH3)4]Br2 Tetramminedibromoplatinum(IV)bomide
[Co(NH3)5CO3]Cl Pentaamminecarbonatocobalt(III)chloride
[Co(H2O)(NH3)5]I3 Pentaammineaquacobalt(III)iodide

Shri Swami Vivekanand Shikshan Sanstha

Kolhapur
 [Cu(NH3)4]SO4 Tetraamminecopper(II)sulphate
[Co(en)3]Cl3 Tris(ethane 1,2diammine)cobalt(III)chloride
[Cr(H2O)4Cl2]Cl Tetraaquadichloridochromium(III)chloride
[Ag(NH3)2]Cl Diamminesilver(I) chloride
IUPAC names of compounds containing complex anions -
Na3[Co(NO2)6] Sodiumhexanitrocobaltate(III)
K3[Al(C2O4)3] Potassiumtrioxalatoaluminate(III)
Na3[AlF6] Sodiumhexafluoroaluminate(III

Shri Swami Vivekanand Shikshan Sanstha

Kolhapur
K4[Fe(CN)6] Potassium hexacyanoferrate(II)
K3[Fe(CN)6] Potassium hexacyanoferrate(III)
Na[Ag(CN)2] Sodium dicyanoargentate(I)

IUPAC names of neutral complexes-

[Co(NO2)3(NH3)3] Tetraamminetrinitrocobalt(III)
Fe(CO)5 Pentacarbonyliron(0)
[Rh(NH3)3(SCN)3] Triamminetrithiocyanatorhodium(III)
Ni(CO)4 Tetracarbonylnickel(0)

Shri Swami Vivekanand Shikshan Sanstha

Kolhapur
Isomerism in co-ordination compounds: Compounds having same
molecular formula but different physical and chemical properties are
called isomers and the phenomenon is called isomerism. It is of two
types:
1] Stereoisomerism.
2] Structural or constitutional isomerism
2] Stereoisomerism: Compounds having same molecular formula but
different spatial arrangement of ligands around the central metal atom are
called stereoisomers and the phenomenon is called stereoisomerism.
It is of two types-
[i] Geometric isomers or Distereoisomers
[ii] Optical isomers or enantiomers
Shri Swami Vivekanand Shikshan Sanstha
Kolhapur
i. Geometrical isomerism:
Geometrcal isomers have nonsuperimposable mirror image.
It is common in compound with co-ordination number 4 and 6.
Complex with co-ordination number 4 have square planer and
tetrahedral geometry.
Co-ordination number 4 :Tetrahedral complex does not show geometrical
isomerism because all ligands are at equidistant to one another
Geometrical isomerism is present in square planer complex.
When similar ligands occupy adjacent position, it is called cis-isomer and
when similar ligands are opposite to each other then it is called trans-
isomer.

Shri Swami Vivekanand Shikshan Sanstha

Kolhapur
Cis & trans isomers in square planar complexes-
Complexes of type MA2B2 & MA2BC type exist exist as
cis & trans isomers.
Example- Pt(NH3)2Cl2

Cl NH3 Cl NH3
Pt Pt
Cl NH3 H3N Cl
Cis isomer trans isomer
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Kolhapur
[Pt(NH3)(H2O)Cl2] - MA2BC type

Cl H2O Cl H2O
Pt Pt
Cl NH3 H3N Cl
cis isomer trans isomer

Shri Swami Vivekanand Shikshan Sanstha

Kolhapur
Cis & trans isomers in octahedral complexes-Complexes of type
MA4B2 , MA4BC & M(AA)2B2 exist as cis & trans isomers.
MA4B2 [Co(NH3)4Cl2] +

Cl + Cl +
H3N Cl H3N NH3
Co Co
H3N NH3 H3N NH3
NH3 Cl
cis isomer trans isomer

Shri Swami Vivekanand Shikshan Sanstha

Kolhapur
MA4BC Type - [Pt(NH3)4ClBr]2+

NH3 2+ Cl 2+
Cl NH3 H3N NH3
Pt Pt
Br NH3 H3N NH3
NH3 Br
Cis isomer trans isomer

Shri Swami Vivekanand Shikshan Sanstha

Kolhapur
[Co(en)2Cl2] , M(AA)2B2 type

Cl Cl
Cl
en Co en Co en

en Cl

Cis isomer trans isomer

Shri Swami Vivekanand Shikshan Sanstha

Kolhapur
ii.Optical isomers[Enantiomers]: The isomers which
rotate the plane polarized light are called optical
isomers. They are d and l types.
Optical isomerism exists in a molecule which is not
superimposable on its mirror image. The condition for
optical isomerism is that a molecule should not have a
plane of symmetry.
Square planar complexes do not show enantiomers
since they have plane & axis of symmetry.
Shri Swami Vivekanand Shikshan Sanstha
Kolhapur
Octahedral compounds with three bidentate ligands, show optical isomerism.
Optical isomerism in octahedral complexes- [Co(en)3]3+

en en

en Co Co en

en en

dextro Mirror laevo

Shri Swami Vivekanand Shikshan Sanstha

Kolhapur
Octahedral compounds with with two bidentate and two monodentate ligands
show optical isomerism. Cis-isomer show optical isomerism because its mirror
image is non-superimposable. Trans-isomer does not show optical isomerism
because its mirror is superimposable
Cl Cl Cl
Cl Cl
en Pt Pt en en Pt en

en en Cl
dextro Mirror laevo
cis- isomer trans- isomer

Shri Swami Vivekanand Shikshan Sanstha

Kolhapur
2] Structural isomerism: Compounds having same molecular
formula but different structures are called structural isomers and
phenomenon is called structural isomerism.
Structural isomerism can be classified into four types.
i] Ionization isomerism ii] Hydrate isomerism
iii] Linkage isomerism iv] Co-ordination isomerism
i. Ionisation isomerism: It is due to exchange of counter ions
with the ligand present inside the co-ordination sphere. They
give different ions in solution.
For example- [Co(NH3)5Br]SO4 and [Co(NH3)5SO4]Br
Shri Swami Vivekanand Shikshan Sanstha
Kolhapur
ii. Hydrate isomerism[solvate isomers when water is solvent]: The isomers differ
in the position of water molecules.
For example- [Cr(H2O)6]Cl3 and [Cr(H2O)5Cl]Cl2.H2O
(I) (II)
In compound (I) water is directly bonded to Cr. In compound (II) water is free solvent
molecule.

iii. Linkage isomerism: It is due to presence two different donor atoms in the same
ligand.
For example-[Co(NH3)5NO2]Cl2 and [Co(NH3)5(ONO)]Cl2

iv. Co-ordination isomerism: It is due to interchange of ligands between two

complex ions.
For example- [Co(NH3)6][Cr(CN)6] and [Cr(NH3)6][Co(CN)6]
(Cationic) (Anionic) (Cationic) (Anionic)
Shri Swami Vivekanand Shikshan Sanstha
Kolhapur
Stability of co-ordination compounds:
The stability of complex depends upon extent of interaction between the metal ions
and ligands.
Ma+ + nLx- [ MLn ]b+
The equilibrium constant ( K ) is called stability constant and is given by
[ MLn ]b+
K=
[Ma+] [Lx-]n
Larger the value of K more stable will be the complex and vice versa.
Factors affecting stability of complexes:
1. Higher the charge and smaller is the radius of ion, greater is the stability of complex.
2. Nature of ligands: Greater the basic strength of the ligand, greater is the stability of
complex.
Shri Swami Vivekanand Shikshan Sanstha
Kolhapur
Bonding in co-ordination compounds:
Valence bond theory: VBT is based on concept of hybridisation.It assumes that
the bonds between metal ion and ligands are covalent co-ordinate.
Features of VBT:
i. A central metal ion in a complex possess vacant s, p and d orbitals.
ii. The number of vacant orbitals provided by the central ion is the same as its co-
ordination number.
iii. Vacant orbitals undergo hybridization to form same number of hybrid orbitals.
iv. Each ligand has at least one orbital containing a lone pair of electrons.
v. Vacant hybrid orbital of the metal ion overlaps with filled orbitals of the ligand.
vi. Geometrical shape of the complex ion depends upon the hybridization of the
metal orbitals.

Shri Swami Vivekanand Shikshan Sanstha

Kolhapur
vii. Greater the overlap stronger is the bond.
viii. If (n-1) d orbitals are used for hybridization the complexes are
called inner orbital or low spin or spin paired complexes. When
n d orbitals are used for hybridization the complexes are
called outer orbital or high spin or spin free complexes.
ix. When central metal atom of the complex contains unpaired
electrons the complex is paramagnetic and if it does not
contain unpaired electrons the complex is diamagnetic in
nature
x. Under the influence of strong ligand, the electrons can be
forced to pair up against Hund’s rule of maximum multiplicity.
Shri Swami Vivekanand Shikshan Sanstha
Kolhapur
Types of hybridisation Geometry

sp hybridisation Linear

sp2 hybridisation Triangular

sp3 hybridisation Tetrahedral

dsp2 hybridisation Square planar

d2sp3 or sp3d2 hybridisation Octahedral

Shri Swami Vivekanand Shikshan Sanstha

Kolhapur
Octahedral complexes-
Structure of [Co(NH3)6]3+ { hexamminecobalt(III)ion} on the basis of VBT-
Atomic number of Co=27
Oxidation state of Co=+3
Ligands= six NH3 (strong)
Electronic configuration of Co & Co2+
Co[Z=27]= 1s2 2s2 2p6 3s2 3p6 3d7 4s2 4p0
Co3+[Z=24]= 1s2 2s2 2p6 3s2 3p6 3d6 4s04p0
Co3+ =

3d 6 4s 0 4p 0
In presence of strong ligand NH3 , 3d electrons are rearranged against Hund’s rule.
Shri Swami Vivekanand Shikshan Sanstha
Kolhapur
Co3+ =

d2sp3 hybridisation

[Co(NH3)6]3+=

d2sp3 hybrid orbitals

six pair of electrons from six NH3 ligands

Shri Swami Vivekanand Shikshan Sanstha

Kolhapur
Complex is formed by d2sp3 hybridisation , hence it is octahedral
complex. It is diamagnetic due to absesence of unpaired electrons.It is
low spin complex because inner d orbitals are used for bonding.
Structure of co-ordination complex [Co(NH3)6]Cl3

NH3 3+
NH3 NH3
Co
NH3 NH3
NH3
Octahedral complex
Shri Swami Vivekanand Shikshan Sanstha
Kolhapur
Structure of [CoF6]3- { hexafluorocobaltate(III)ion} on the basis of VBT-
Atomic number of Co=27
Oxidation state of Co=+3
Ligands= six F -(Weak)
Electronic configuration of Co & Co2+
Co[Z=27]= 1s2 2s2 2p6 3s2 3p6 3d7 4s2 4p0
Co3+[Z=24]= 1s2 2s2 2p6 3s2 3p6 3d6 4s04p0

Co3+ =
3d 6 4s0 4p 0 4d 0

sp3d2 hybridisation
Shri Swami Vivekanand Shikshan Sanstha
Kolhapur
3d orbital is not involved in hybridisation. F- is weak ligand and can not force
3d electrons to pair up.

[CoF6]3- =

3d6 sp3 d2 hybrid orbitals

six pair of electrons from six F- ligands
Complex is formed by sp3d2 hybridisation , hence it is octahedral complex.
It is paramagnetic due to presence of unpaired electrons.It is high spin
complex.

Shri Swami Vivekanand Shikshan Sanstha

Kolhapur
Structure of co-ordination complex [CoF6]3-

F 3-
F F
Co
F F
F
Octahedral complex

Shri Swami Vivekanand Shikshan Sanstha

Kolhapur
Tetrahedral complex-
Structure of [Ni(Cl)4]2- { tetrachloronickelate (II)ion} on the basis of VBT-
Atomic number of Ni=28
Oxidation state of Ni=+2
Ligands= four Cl (Weak)
Electronic configuration of Ni & Ni 2+
Ni [Z = 28] = 1s2 2s2 2p6 3s2 3p6 3d8 4s2 4p0
Ni2+ [Z = 26] = 1s2 2s2 2p6 3s2 3p6 3d8 4s0 4p0
Ni undergoes sp3 hybridisation by mixing one 4s & three 4p orbitals to form
four sp3hybrid orbitals.

Shri Swami Vivekanand Shikshan Sanstha

Kolhapur
Ni 2+ =

3d8 4s0 4p0

sp3 hybridisation

[Ni(Cl)4]2- =

Four sp3 hybrid orbitals

Four pair of electrons from four Cl- ligands.
Complex is formed by sp3 hybridisation , hence it is
tetrahedral. It is paramagnetic due to presence of two unpaired electrons.
It is high spin complex because metal can use 4s & 4p orbitals for bonding.
Shri Swami Vivekanand Shikshan Sanstha
Kolhapur
 Cl 2-

Ni

Cl Cl
Cl

Tetrahedral

Shri Swami Vivekanand Shikshan Sanstha

Kolhapur
Square planar complex-
Structure of [Ni(CN)4]2- { tetracyanonickelate (II)ion} on the basis of VBT-
Atomic number of Ni=28
Oxidation state of Ni=+2
Ligands= four CN (Strong)
Electronic configuration of Ni & Ni 2+
Ni[Z=28]= 1s2 2s2 2p6 3s2 3p6 3d8 4s2 4p0
Ni2+[Z=26]= 1s2 2s2 2p6 3s2 3p6 3d8 4s0 4p0
In presence of strong ligand CN , 3d electrons are rearranged against Hund’s rule.

Ni2+ =
3d 8 4s 0 4p 0

Shri Swami Vivekanand Shikshan Sanstha

Kolhapur
Ni2+ =
3d 4s 4p

dsp2 hybridisation

[Ni(CN)4]2-=

Four dsp2 hybrid orbitals

Four pair of electrons from four CN ligands

Shri Swami Vivekanand Shikshan Sanstha

Kolhapur
 Complex is formed by dsp2 hybridisation , hence it is square planar complex. It
is diamagnetic due to absesence of unpaired electrons.It is low spin complex
because metal can use 3d , 4s & 4p orbitals for bonding.
NC CN 2-
Ni
NC CN

Square planar complex

Limitations of VBT :
[1] It does not explain strong field & weak field nature of ligands.
[2] It does not explain colour of coordination compounds.
[3] Structure predicted from VBT always not match with structure determined from
experiments

Shri Swami Vivekanand Shikshan Sanstha

Kolhapur
Crystal field theory: Ligands are treated as point charges. The
interaction between metal ion & ligand is electrostatic.
In the presence of electric field of the ligands, the five degenerate d-
obitals of the metal ion split into two different sets of orbitals
having different energies. This is called crystal field splitting.
For example in case of octahedral complexes, the five d-orbitals
split into two sets:
i. Two orbitals (dx2-y2 and dz2) become of higher energy and are
called egorbitals.
ii. three orbitals (dxy dyz dzx ) become of lower energy are called
t2g orbitals.

Shri Swami Vivekanand Shikshan Sanstha

Kolhapur
 eg
dx2-y2 dz2
3/5Δ0

Δo
---………………………………………………………..

2/5Δ0

t 2g
dxy dyz dzx

The energy difference between two sets of energy levels is called crystal field spiltting energy and is
represented as Δo .

Shri Swami Vivekanand Shikshan Sanstha

Kolhapur
The ligands which cause greater crystal field spliting are called
strong ligands while the ligands which cause lesser crystal field
spliting are called weak ligands.
In strong field ligands donor atoms are C,N & P
In weak field ligands donor atoms are halogens, oxygen &
Sulphur.
The ligands can be arranged in decreasing order of crystal field splitting
(Δo) energy and it is called spectro-chemical series.
I- < Br- < Cl- < S2- < F- <OH- < C2O42-< H2O < NCS- < EDTA< NH3 < en < CN- < CO
Ligands before H2O are weak field ligands & after H2O are strong field ligands.

Shri Swami Vivekanand Shikshan Sanstha

Kolhapur
In tetrahedral complexes the splitting is reverse as

t2g

2/5 Δt dxy dyz dzx

………………………………………….. Δt

3/5Δt

eg
dy2 dz2

Δt is generally small and it is found to be Δt = 4/9 Δo

Shri Swami Vivekanand Shikshan Sanstha

Kolhapur
Distribution of d-electrons in t2g and eg orbitals in
octahedral complexes and tetrahedral complexes:
The first three electrons enter the lower energy t2g orbital. The
entery of further electrons is governed by the magnitude of
pairing energy (p).
(a) In case of weak ligands Δo < p, hence the electrons will avoid
pairings and the filling of orbitals will be in the order

t2g1 2 3 eg 4 5 t2g6 78 eg 9 10

Shri Swami Vivekanand Shikshan Sanstha

Kolhapur
(b) In case of strong ligands Δo>p hence the electrons will prefer
pairing and the filling of orbitals will be in the order
t2g1 2 3 4 5 6 eg 7 8 9 10
Note: Weak ligands give high spin complexes and strong ligands give
low spin complexes.
For tetrahedral complexes the filling will as follows-
In case of weak ligands
eg 1 2 t2g 3 4 5 eg 6 7 t2g 8 9 10

In case of strong ligands

eg 1 2 3 4 t2g 5 6 7 8 9 10

Shri Swami Vivekanand Shikshan Sanstha

Kolhapur
Limitations of crystal field theory:
i. CFT considers only the metal ion in d-orbital and gives no consideration to
other orbitals such as ‘s’ and ‘p’ orbitals .
ii. It considers only the ionic bond between metal and ligand.
Covalency cannot be explained by CFT.
iii. It can not explain why some ligands are strong & some are weak.
Colour in co-ordination compounds:
According to CFT the ligand splits the d- orbitals into two sets which differ
in their energies. On absorption of appropriate wavelength from white light,
the electrons are excited from the d-orbitals of lower energy to those of
higher energy. The colour of complex is complementary to that which is
absorbed.

Shri Swami Vivekanand Shikshan Sanstha

Kolhapur
Applications of co-ordination compounds-
1.In Biology-Chlorophyll present in plants is a complex of Mg.Haemoglobin
present in blood is a complex of iron. They are important in biological
processes
2. In medicines-
[a] Pt complex cisplatin is used in treatment of cancer.
[b] EDTA is used in treatment of lead poisoning
3. To estimate hardness of water-
Hard water contains Ca2+ & Mg2+ ions. EDTA forms complexes with these ions
. It is used to estimate hardness of water.
4. In electroplating-
Cyanide complexes K[Ag(CN)2] & K[Au(CN)2] find applications
in electroplating. Metal atoms form protective layer.
Shri Swami Vivekanand Shikshan Sanstha
Kolhapur
Previously asked questions in H.S.C. Board examination-
Feb.-2019
Q.1 What is effective atomic number? Calculate effective atomic number of
copper(Z=29) in [Cu(NH3)4]2+ [3 Marks]
July-2019
Q.1 Write IUPAC name of [Pt(en)2Cl2]2+ complex ion. [ 1 Mark]
Q.2 Explain linkage isomerism. [ 2 Marks]
Feb.-2020
Q.1 Calculate the effective atomic number (e.a.n.) of copper in
[Cu(NH3)4]2+( Zof Cu=29 )
Explain ionisation isomerism in coordination compounds with a suitable
example . [ 3 Marks]

Shri Swami Vivekanand Shikshan Sanstha

Kolhapur
Deleted portion due to COVID-19 for Feb/ March2021

Chapter No. & Name Page Deleted & Non-Evaluative

No. portion
204 9.9.6 Ctystal field theory
9. Coordination compounds 205 9.9.7 Factors affecting crystal
field spiliting parameter

205 9.9.8 Colour of octahedral

complexes
206 9.9.9 Tetrahedral complexes
[Page No.- 206]

Shri Swami Vivekanand Shikshan Sanstha

Kolhapur
 श्री स्वामी वििेकानंद विक्षि संस्था, कोल्हापूर.
रसायनिास्त्र अभ्यास मंडळ

E – Content Prepared by -
Name of the teacher :- Prof. Annaso Nemgonda Patil.
Name of the college :- Vivekanand college Kolhapur Dist :- Kolhapur.
Mobile Number :- 9049512108
E- mail Address :- [email protected]

Shri Swami Vivekanand Shikshan Sanstha

Kolhapur