CO - ORDINATION

COMPOUNDS
 DOUBLE SALT:
 It is the salt which contains two salts in equimolar ratio.
Ex.: Mohr’s salt ⟹FeSO4.(NH4)2SO4.6H2O
Potash alum: K2SO4. Al2(SO4)3 . 24 H2O
 It is prepared by mixing the saturated solutions to two
salts followed by evaporating to dryness.
K2SO4 (aq.) + Al2(SO4)3 (aq.) + 24 H2O

K2SO4. Al2(SO4)3 . 24 H2O

 COMPLEX COMPOUNDS
The compound formed when at least one lone pair of electrons are
accepted by a metal is called as complex compound. Ex.:
[Co (en)3]Cl3

 TERMS USED IN A COMPLEX COMPOUND:

 LIGAND:
The atom / ion / molecule which can donate a lone pair of electron
to a metal atom or ion is called as ligand.
 Types of ligands: (on the basis of charge present on it)
a) Positive ligand: The ligand having a net positive charge is called as
positive ligand. Ex.: NO2+.
b) Negative ligand: The ligand having a net negative charge is called as
negative ligand. Ex.: C2O42-.
c) Neutral ligand: The ligand having no net charge is called as neutral
ligand. Ex.: H2O.
 Types of ligands: (on the basis of no. of atoms which donate lone
pair of electron):
a) Monodentate ligand:
The ligand which has only one atom which can donate lone pair of
electrons is called as monodentate ligand. Ex.:
b) Bidentate ligand:
The ligand which has two atoms which can donate lone pair of
electrons is called as bidentate ligand. Ex.:
c) Polydentate ligand:
The ligand which has more than two atoms which can donate lone
pair of electrons is called as polydentate ligand. Ex.: EDTA.
 SOME IMPORTANT LIGANDS:
Symbol Name Symbol Name
Cl- Chlorido NCS- Isocyanate
Br- Bromido ONO⁻ Nitrito
CN- Cyano NO2- Nitro
O2- Oxo SO32- Sulphito
O22- Peroxo H2O Aquo / Aqua
OH- Hydroxo NH3 Ammine
S2- Sulphido CS thiocarbonyl
N3- Nitrido CO carbonyl
P3- Phosphido NO nitrosyl
CO32- Carbonato SCN- Thiocyanate
C2O42- Oxalato NO+ Nitrosonium
SO42- Sulphato H2NNH3+ Hydrazinium
NO3- Nitrato NH2- Imido
CH3COO- Acetato en Ethylene
diammine
 BRIDGE LIGAND:
The ligand which donates two lone pairs of electrons to two metals
simultaneously, is called as bridge ligand.

 CHELATION:
If a ligand simultaneously donates two lone pairs of electrons to
the same metal, it is called as chelation.
 CENTRAL METAL:
The metal which accepts lone pair of electrons from the ligands is
called as central metal.
 CO – ORDINATION SPHERE:
The central metal and ligands are togather called as co – ordination
number.
 CO – ORDINATION NUMBER:
The number of lone pair of electrons accepted by the central metal
atom or ion is called as co – ordination number.

[ Ni (NH3)6]Cl2
Q. Which of the following ligands is expected to be bidentate

[NEET 1994]
a. CH3NH2 b. CH3 – C ≡ N
c. Br d. C2O42 ͞

Q. EDTA is a [NEET
2021]
(a) Unidentate ligand.
(b) Bidentate ligand with two “N” donor atoms.
(c) Tridentate ligand with three “N” donor atoms.
(d) Hexadentate ligand with four ‘O” & two “N” donor atoms.
Q. The co – ordination number and oxidation state of Cr in
K3[Cr(C2O4)3] are respectively [NEET
1995]
a. 4 & +2 b. 6 & +3
c. 3 & +3 d. 3 & 0

Q. Co – ordination number of Ni in [Ni(C2O4)3]4 ͞

a. 3 b. 6
c. 4 d. 2

Q. The sum of co – ordination number and oxidation number of

metal
a. 7 M in the complex [M(en)2b.(C82O4)]Cl is [NEET2015]
c. 9 d. 6
 RULES FOR I.U.P.A.C. NOMENCULATURE:
 If any metal is present left to the co – ordination sphere , it
should be named first without any numeral prefix.
 Now, the ligands should be named in an alphabetical order
with a numeral prefix (di / tri …..etc ) indicating their number
without taking in account the charges.
 Now, the metal present in the co – ordination sphere should be
named along with it’s oxidation number in roman word.
 The name of the metal of the co – ordination sphere of the
anionic co – ordination sphere should last in the suffix “-ate”.
 The metal of the co – ordination sphere of the cationic / neutral
co – ordination sphere should named as such.
 Any anion present right to the co – ordination sphere should be
named at the last.
 The name of the complex ion should last in the word “ion”.
Q. Write the IUPAC name of the following compounds:
 [Cr(NH3)3Cl3]
 K3[Fe(CN)6]
 [CoBr2(en)2]+
 [Co(NH3)4 (H2O) Cl]Cl2.
 [Cr Cl2 (en)2]Cl.
 [CoCl4]2ˉ.
 [Ni(CN)4]2ˉ
 [Cr(H2O)2(C2O4)2]ˉ.
1) When a co – ordination compound [CoCl3.6NH3] is mixed with
AgNO3, 3 moles of AgCl is precipitated per mole of compound.
Write
a) Structural formula of the complex.
b) IUPAC name of the complex.
Q. Write the formulae of the following compounds:
 Hexa – ammine – cobalt(III) – chloride.
 Potassium – tetrachlorido – nickelate(II)
 Sodium – dicyanidoaurate(I)
 Tetra – ammine – chlorido – N – nitrito – platinum (IV) –
sulphate
 Iron(III)hexacyanoferrate(II).
Q. The hypothetical complex triamminediaquachloridocobalt(III)
chloride can be represented as [2002]
a) [CoCl(NH3)3(H2O)2]Cl2
b) [Co(NH3)3(H2O) Cl3]
c) [CoCl(NH2)3(H2O)2]
d) [CoCl(NH3)3(H2O)3]Cl2
Q. An excess of AgNO3 is added to 100 ml of 0.01M solution of
dichloridotetraaquachromium(III) chloride. The number of
moles of AgCl precipitated would be [2013]
e) 0.001
f) 0.002
g) 0.003
h) 0.01
 Q. The IUPAC name of the complex [Ag(H2O)2] [Ag(CN)2] is
[NEET
2022]
a) Dicynidosilver(I) diaquaargentate(I)
b) Diaquasilver (I) dicyanidoargentate(I)
c) Dicynidosilver(II) diaquaargentate(II)
d) Diaquasilver(II) dicynidoargentate (II)
 EFFECTIVE ATOMIC NUMBER (E. A. N.):
The number of electrons present around a central metal atom or ion
after formation of a complex compound or ion is called as E. A. N.

 EXPRESSION FOR E. A. N.:

E. A. N. = [(Z – O.N.) + (2 × Co – ordination no.)]
Where Z = Atomic no. of the element

 NOTE: The complex compound / ion is more stable when the value
of E.A.N. is equal to the atomic number of any noble gas.
 ISOMERISM IN COMPLEX COMPOUNDS:
The phenomenon in which two or more compounds have same
molecular formula but different structure or spatial arrangement is
called as isomerism.
 TYPES OF ISOMERISM:
1) Strucutural isomerism
2) Stereo isomerism
1) STRUCTURAL ISOMERISM:
The isomerism in which the isomers have different structural
formula but same molecular formula is called as structural
isomerism.
 Types of structural isomerism:
a) Ionisation isomerism:
The isomerism in which the isomers which have same molecular
formula and have produce different types of ions on dissociation is
called as ionisation isomerism.
Ex.: [Co(NH3)5Br]SO4 & [Co(NH3)5SO4]Br
b) Linkage isomerism:
The isomerism in which the isomers which have same molecular
formula and have difference in linkage atom of the ligand with central
metal is called as linkage isomerism.
Ex.:[Co(NH3)5NO2]2+ & [Co(NH3)5ONO]2+

c) Hydration isomerism:
The isomerism in which the isomers which have same molecular
formula and have difference in water molecule as ligand is called as
hydration isomerism.
Ex: [Co(H2O)6]Cl3 & [Co(H2O)5 Cl]Cl2.H2O

d) Co – ordination isomerism:
The isomerism in which the isomers have same molecular formula
and have difference in co – ordinaion sphere is called as co -
ordination isomerism.
Ex: [Co(NH3)6][Cr(CN)6] & [Cr(NH3)6][Co(CN)6]
2) STEREO ISOMERISM:
The isomerism in which two compounds have same molecular
formula but difference in their spatial arrangement of ligands
around the central metal is called as stereoisomerism.

 Types of stereo isomerism:

a) Geometrical isomerism:
The isomerism in which the isomers have same molecular formula
but difference in geometry is called as geometrical isomerism.
Ex.:
Coditions for geometrical isomerism:
1) Compex should be heteroleptic complex in which at least two
ligands should be defferent.
2) Complex should not be tetrahedral.
 Geometrical isomerism in square planner complexes having
monodentate ligands only:
Case 01: Type [MA2B2]
Ex.:
Case 02: Type [MA2BC]
[Pt (Py)2 NH3 Cl]

Case 03: Type [M ABCD]

[Pt (Py) (NH3) (H2O) (NO2)]

 Geometrical isomerism in square planner complexes

having bidentate ligands only:
Case 01: Type [M (AB)2]
Ex.: [Pt (Gly)2] [Gly = 2HN – CH2 – COO ̅]
 Geometrical isomerism in octahedral complexes having
monodentate ligands only:
Case 01: Type [MA4B2]
[Co (NH3)4Cl2] ̅

Case 02: Type [M A3B3]

[Co (NH3)3 Cl3]

 Geometrical isomerism in octahedral complexes having

bidentate ligands :
Case 01: Type [M (AA)2 B2]
Ex.: [Co (en)2 Cl2]
b) Optical isomerism:
The isomerism in which the compounds are mirror image of each
other is called optical isomerism.
Ex.:

Enantiomers: The compounds which are optical isomers of each other

are called as enantiomers.
 Conditions for optical isomerism:
⇒ Complex should be chiral.
⇒ Complex should not be square planner.
 Characteristics of optical isomers:
⇒ They have same physical and chemical properties but they have
different behaviour towards plane polarised light.
⇒ One of the enantimer rotates the plane polarised light toward left /
in anti clockwise direction called l – form / leavo form while the
other enantiomer rotates the light toward right or in clockwise
direction called as d – form or dextro form.
 Racemic mixture: It is equimolar mixture of l form and d – form of
enantimers of an optically active substance.
 Optical isomerism in octahedral complexes:
Case 01: Optical isomerism in complexes of type [M(AA)3]:

Ex. [Co (en)3]3+

Case 02: Optical isomerism in complexes of type [M(AA)2 B2]:
Ex.: [Co (en)2 Cl2]+

Case 03: Optical isomerism in complexes of type [M(AA)2 B C]:

Ex.: [Co (en)2 NH3 Cl]2+
 PREVIOUS YEAR QUESTIONS:
1) Three geometrical isomers are possible for [Co(en)H2O)2
(NH3)2]3+. Draw the molecular structures of all three isomers
and indicate which one of them is chiral?
2) What type of isomerism is shown by the complex
[Co(NH3)5(SCN)]2+?
3) Draw the geometrical isomers of the complex [Pt(en)2Cl2]2+
which is optically inactive.
4) Write down the IUPAC name of the complex [Pt(en)2Cl2]2+.
which type of isomerism is shown by the complex?
5) What type of isomerism is exhibited by the complex
[Co(en)3]3+
6) Give an example of linkage isomerism.
 VALANCE BOND THEORY:
The main aspects of valance bond theory are as follows:
 The central metal atom / ion have a number of vacant orbitals in the
s, p, and d sub – shells.
 The ligand should have at least one lone pair of electrons in its
orbitals to donate to the central atom / ion.
 The full filled orbitals of ligand overlap on the empty orbital of
central atom / ion.
 The non – bonding metal electrons occupy the inner d – orbitals
which are not hybridised.
 Under the influence of strong ligand [CN¯ , CO etc.] the unpaired
electrons are forced to pair up against Hund’s rule.
 Limitations of valance bond theory:
 It can not explain the thermodynamic stability of the complex
compound.
 It can not explain the magnetic properties of a complex compound.
 WERNER’S THEORY OF COMPLEX COMPOUND:
The main aspects of Werner’s theory are as follows:
 The central metal atom / ion has two types of valancies: Primary
valancy and secondry valancy.
 All the primary valancies are satisfied by anions.
 All the secondary valancies are satisfied by ligands.
 The primary valancies are non directional and denoted by dotted
lines (……….) and all the secondary valancies are directional and
shown by solid lines ( ).
 Limitations of Werner’s theory:
 It can not explain the directional nature of the bonding between
ligand and central metal.
 Only some elements of d – block have tendency to form complex
compound. This fact can not be explained by Werner’s theory.
 This theory can not magnetism and stereo isomerism in the
complex compound.
 VALANCE BOND THEORY:
The main aspects of valance bond theory are as follows:
 The central metal atom / ion have a number of vacant orbitals in the s, p,
and d sub – shells.
 The ligand should have at least one lone pair of electrons in its orbitals to
donate to the central atom / ion.
 The full filled orbitals of ligand overlap on the empty orbital of central
atom / ion.
 The non – bonding metal electrons occupy the inner d – orbitals which
are not hybridised.
 Under the influence of strong ligand [CN¯ , CO etc.] the unpaired
electrons are forced to pair up against Hund’s rule.
 Limitations of valance bond theory:
 It can not explain the thermodynamic stability of the complex compound.
 It can not explain the magnetic properties of a complex compound.
 PREVIOUS YEAR QUESTIONS BASED ON VALANCE BOND THEORY:
1) Write the co – ordination number and oxidation state of
platinum in complex [Pt(en)2Cl2]. [2018]
2) Write the hybridization and number of unpaired electrons in
the complex [CoF6]3ˉ. [2017]
3) For the complex [Fe(H2O)6]3+, write the hybridization,
magnetic character and spin of complex. [2016]
4) Write the name, hybridization, the shape and the magnetic
behavior of the following complexes: [2010]
a) [CoCl4]2ˉ.
b) [Ni(CN)4]2ˉ
c) [Cr(H2O)2(C2O4)2]ˉ.
 CRYSTAL FIELD THEORY :
The main aspects of crystal field theory are as follows:
 The ligands are point charges and there is electrostatic force of
attraction between ligands and central atom / ion.
 The five d – orbitals of the isolated gaseous central metal atom / ion
have same energy.
 The d – orbitals are degenerated in spherically symmetrical field of
negative charges which surround the central metal.
 When the ligands approach the central metal, the energy of d –
orbitals increase and finally they split into two sets of orbitals: eg &
t2g sets.
 The pattern of splitting of the orbitals depends upon the nature of
crystal field.
 It helps to determine the energy difference between the orbitals,
magnetic moment etc.
 The energy difference between the eg & t2g sets of orbitals depends
upon the strength of the ligands.
The order of strengths of ligands are as follows:
I¯ < Br¯ < S2¯ < SCN¯ < Cl¯ < F¯ < OH¯ < C2O42¯ < O2¯ < H2O < NCS¯ < NH3 <
en < NO2¯ < CN¯ < CO
 NOTE:
 In the case of octahedral complex , the energy of eg sets of orbitals is
greater than t2g sets of orbitals.

 In the case of tetrahedral complex, the energy of t2g sets of orbitals

is greater than eg sets of orbitals.
 If the energy difference between the eg & t2g sets of orbitals is
greater, the electrons will first prefer to stay in the orbitals of lower
energy and when the lower orbitals become full filled the next
electron will go in the orbitals of heigher energy and so they form
low spin complex.

 If the energy difference between the eg & t2g sets of orbitals is

smaller, the electrons go in the orbitals of heigher energy without
pairing up in lower energy orbitals and so they form high spin
complex.
 PREVIOUS YEAR QUESTIONS BASED ON CRYSTAL FIELD
THEORY:
1) Why is [NiCl4]2ˉ is paramagnetic? [2017]
2) Why are low spin tetrahedral complex rarely obtained?
[2017]
3) Why is [Ni(CN)4]2ˉ is paramagnetic but [Ni(CO)4] is
diamagnetic? [2014]
4) Explain the following: [2012]
a) The π – complexes are known for transition elements only.
b) Ni(II) does not form low spin octahedral complxes.
c) [Fe(CN)6]4ˉ and [Fe(H2O)6]2+ are of different colours in dilute
solutions.
 FACTORS INFLUENCING THE ORBITAL SPLITTING ENERGY:
 Oxidation states of the central metal atom / ion:
greater the oxidation number of the central metal, greater will be the
energy difference between eg & t2g sets of orbitals.

 Position of the central metal in the periodic table:

Lower the position of the metal in periodic table, greater will be the
energy difference between the eg & t2g sets of orbitals.

 Strength of ligand:
Stronger the ligand, greater will be the energy difference between eg &
t2g sets of orbitals.

 Geometry of the complex:

It has also enfluence on the energy difference between eg & t2g sets of
orbitals.
 MAGNETIC PROPERTIES IN CO – ORDINATION COMPOUNDS:
The complex compound in which the central metal having at least
one unpaired electron is paramagnetic.
The magnetic moment of a complex compound can be expressed as
µ = √n(n+2)
Where n = No. of unpaired electrons.
 COLOUR IN COMPLEX COMPOUNDS:
When light falls on the complex compound, a part of the
electromagnetic wave is absorbed by the electrons of eg or t2g sets of
orbitals. The rest of the waves are released which causes colour in
the complex compounds.
 METAL CARBONYLS:
The compound of a metal of d – block with carbon monoxide /
carbonyl group is called as metal carbonyl.
Ex.: [Ni(CO)4]
 Preparation of metal carbonyls:
Metal carbonyls can be prepared by direct combination of metal
with carbon monoxide under suitable condition of temperature
pressure and catalyst.
Ni + 4 CO [Ni(CO)4]
 Properties of metal carbonyls:
 They are mostly solids and a few are liquids.
 They are either colourless or light coloured.
 They are volatile.
 They are toxic.

 Bonding in metal carbonyls:

The bonding in metal carbonyls can be explained on the basis of
molecular orbital theory.
There are two types of bonding present in metal carbonyls:
First of all overlapping of empty orbital of metal occurs with filled
orbital of carbonyl group.

The next overlap is between filled d – orbital of metal with empty anti -
bonding orbital of carbonyl group called as metal – carbonyl back –
bonding.