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CO – ORDINATION COMPOUNDS ⮚ Types of ligands: (on the basis of no. of atoms which
donate lone pair of electron):
By: Nagendra Kumar
a) Monodentate ligand:
❑ DOUBLE SALT:
The ligand which has only one atom which can donate lone
It is the salt which contains two salts in equimolar ratio.
pair of electrons is called as monodentate ligand. Ex.: NH3.
Ex.: Mohr’s salt ⟹FeSO4.(NH4)2SO4.6H2O
Potash alum: K2SO4. Al2(SO4)3 . 24 H2O b) Bidentate ligand:
⇒ It is prepared by mixing the saturated solutions to two The ligand which has two atoms which can donate lone
salts followed by evaporating to dryness. pair of electrons is called as bidentate ligand. Ex.: C2O42-.
K2SO4 (aq.) + Al2(SO4)3 (aq.) + 24 H2O
K2SO4. Al2(SO4)3 . 24 H2O c) Polydentate ligand:

The ligand which has more than two atoms which can
❑ COMPLEX COMPOUNDS donate lone pair of electrons is called as polydentate ligand. Ex.:
The compound formed when at least one lone pair of EDTA.
electrons are accepted by a metal is called as complex compound.
Ex.: [Co (en)3]Cl3 ❑ SOME IMPORTANT LIGANDS:

❑ TERMS USED IN A COMPLEX COMPOUND: ❑ BRIDGE LIGAND:

❖ LIGAND: The ligand which donates two lone pairs of electrons to two
The atom / ion / molecule which can donate a lone pair of metals simultaneously, is called as bridge ligand.
electron to a metal atom or ion is called as ligand.
⮚ CHELATION:
⮚ Types of ligands: (on the basis of charge present on it)
If a ligand simultaneously donates two or more lone pairs
a) Positive ligand: The ligand having a net positive charge is of electrons to the same metal, it is called as chelation.
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.

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❖ CENTRAL METAL: ▪ Any anion present right to the co – ordination sphere

The metal which accepts lone pair of electrons from the should be named at the last.
ligands is called as central metal.
▪ The name of the complex ion should last in the word
❖ CO – ORDINATION SPHERE: “ion”.

The central metal and ligends are together called as co – ❑ EFFECTIVE ATOMIC NUMBER (E. A. N.):
ordination number.
The number of electrons present around a central
❖ CO – ORDINATION NUMBER: metal atom or ion after formation of a complex compound
or ion is called as E. A. N.
The number of ligands bonded to the central metal atom or
ion is called as co – ordination number. ⮚ EXPRESSION FOR E. A. N.:

[ Ni (NH3)6]Cl2 E. A. N. = [(Z – O.N.) + (2 × No. of lone pair accepted)]

❑ RULES FOR I.U.P.A.C. NOMENCULATURE: Where Z = Atomic no. of the element

▪ If any metal is present left to the co – ordination sphere ⮚ NOTE: The complex compound / ion is more stable when
, it should be named first without any numeral prefix. the value of E.A.N. is equal to the atomic number of any
noble gas.
▪ Now, the ligands should be named in an alphabetical
order with a numeral prefix (di / tri …..etc ) indicating ❑ ISOMERISM IN COMPLEX COMPOUNDS:
their number without taking in account the charges. The phenomenon in which two or more compounds have
same molecular formula but different structure or spatial
▪ Now, the metal present in the co – ordination sphere
arrangement is called as isomerism.
should be named along with it’s oxidation number in
roman word. ❖ TYPES OF ISOMERISM:
1) Strucutural isomerism
▪ The name of the metal of the co – ordination sphere of
2) Stereo isomerism
the anionic co – ordination sphere should last in the
suffix “-ate”. 1) STRUCTURAL ISOMERISM:
The isomerism in which the isomers have different
▪ The metal of the co – ordination sphere of the cationic
structural formula but same molecular formula is called as
/ neutral co – ordination sphere should named as such.
structural isomerism.

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⮚ Types of structural isomerism: arrangement of ligands around the central metal is called as
stereoisomerism.
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

⮚ Types of stereo isomerism:
b) Linkage isomerism: a) Geometrical isomerism:
The isomerism in which the isomers which have The isomerism in which the isomers have same molecular
same molecular formula and have difference in linkage formula but difference in geometry is called as geometrical
atom of the ligand with central metal is called as linkage isomerism.
isomerism.
Ex.:
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. 2. Optical isomerism:
Ex: [Co(H2O)6]Cl3 & [Co(H2O)5 Cl]Cl2.H2O The isomerism in which the compounds are mirror
image of each other is called optical isomerism.
d) Co – ordination isomerism:
The isomerism in which the isomers have same Ex.:
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 ❑ WERNER’S THEORY OF COMPLEX COMPOUND:
The main aspects of Werner’s theory are as follows:

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▪ The central metal atom / ion has two types of valancies: ▪ The non – bonding metal electrons occupy the inner d –
Primary valancy and secondry valancy. orbitals which are not hybridised.

▪ All the primary valancies are satisfied by anions. ▪ Under the influence of strong ligand [CN¯ , CO etc.] the
unpaired electrons are forced to pair up against Hund’s
▪ All the secondary valancies are satisfied by ligands.
rule.
▪ 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.
⮚ Limitations of valance bond theory:
▪ Only some elements of d – block have tendency to form
complex compound. This fact can not be explained by ▪ It can not explain the thermodynamic stability of the
Werner’s theory. complex compound.

▪ This theory can not magnetism and stereo isomerism in the ▪ It can not explain the magnetic properties of a complex
complex compound. compound.

❑ VALANCE BOND THEORY: ❑ CRYSTAL FIELD THEORY :

The main aspects of valance bond theory are as follows: The main aspects of crystal field theory are as
follows:
▪ The central metal atom / ion have a number of vacant
orbitals in the s, p, and d sub – shells. ▪ The ligands are point charges and there is electrostatic
force of attraction between ligands and central atom / ion.
▪ The ligand should have at least one lone pair of electrons in
its orbitals to donate to the central atom / ion. ▪ The five d – orbitals of the isolated gaseous central metal
atom / ion have same energy.
▪ The full filled orbitals of ligand overlap on the empty orbital
of central atom / ion. ▪ The d – orbitals are degenerated in spherically symmetrical
field of negative charges which surround the central metal.

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▪ When the ligands approach the central metal, and becomes

assymetrical, 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.

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⮚ If the energy difference between the eg & t2g sets of orbitals ML + L ⇌ [ML2], K2 = [ML2]/[ML][L]
is smaller, the electrons go in the orbitals of heigher energy ML2 + L ⇌ [ML3], K3 = [ML3]/[ML2][L]
without pairing up in lower energy orbitals and so they ML3 + L ⇌ [ML4], K4 = [ML4]/[ML3][L]
form high spin complex.
The overall stability constant is expressed as
❑ FACTORS INFLUENCING THE ORBITAL SPLITTING
β 4 = K1 × K2 × K3 × K4
ENERGY:
▪ Oxidation states of the central metal atom / ion:
β4 = [ML] × [ML2] × [ML3] × [ML4]
Greater the oxidation number of the central metal, greater
[M][L] [ML][L] [ML2][L] [ML3][L]
will be the energy difference between eg & t2g sets of
orbitals. β4 = [ML4]
▪ Position of the central metal in the periodic table: [M][L]4

Lower the position of the metal in periodic table, greater ▪ General formula for overall stability constant having n
will be the energy difference between the eg & t2g sets of number of ligands:
orbitals. βn = K1 × K2 × K3 × K4 ……….. ×Kn
▪ Strength of ligand:
▪ Overall dissociation constant = 1/ βn
Stronger the ligand, greater will be the energy difference
between eg & t2g sets of orbitals. ❑ FACTORS INFLUENCING THE STABILITY OF COMPLEXES:
▪ Oxidation states of the central metal atom / ion:
▪ Geometry of the complex:
Greater the oxidation number of the central metal, greater
It has also enfluence on the energy difference between eg & will be the stability of the complex.
t2g sets of orbitals.
Ex.: [Fe(CN)6]4ˉ is less stable than [Fe(CN)6]3ˉ

▪ Size of the central metal:

❑ STABILITY OF COMPLEXES:
Lower the position of the metal in periodic table, greater
Greater the value of overall stability constant, greater will
will be the energy difference between the eg & t2g sets of
be the stability of the complex compound/ion.
Ex. orbitals.
M + L ⇌ [ML], K1 = [ML]/[M][L] ▪ Strength of ligand:

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Stronger the ligand, greater will be the greater will be the The compound of a metal of d – block with carbon
stability of the complex. monoxide / carbonyl group is called as metal carbonyl.

Ex.: [Fe Cl6]3ˉ is less stable than [Fe(CN)6]3ˉ Ex.: [Ni(CO)4]

▪ Chelating ligand: ❖ Preparation of metal carbonyls:

Presence of chelating ligand produces more stability in the
Metal carbonyls can be prepared by direct
complex.
combination of metal with carbon monoxide under suitable
Greater the number of chelating ligand , greater will be the
condition of temperature pressure and catalyst.
stability.
Ex.: The stability order in the following complexes are as Ni + 4 CO [Ni(CO)4]
follows:
[Cr(en)3]3+ > [Cr(en)2 (NH3)2]3+ > [Cr(en) (NH3)4]3+> ❖ Properties of metal carbonyls:
[Cr(NH3)6]3+ ▪ They are mostly solids and a few are liquids.
❑ MAGNETIC PROPERTIES IN CO – ORDINATION ▪ They are either colourless or light coloured.
COMPOUNDS:
The complex compound in which the central metal having ▪ They are volatile.
at least one unpaired electron is paramagnetic.
▪ They are toxic.
The magnetic moment of a complex compound can
❖ Bonding in metal carbonyls:
be expressed as The bonding in metal carbonyls can be explained on
µ = √n(n+2) the basis of molecular orbital theory.

Where n = No. of unpaired electrons. There are two types of bonding present in metal carbonyls:

❑ COLOUR IN COMPLEX COMPOUNDS: First of all overlapping of empty orbital of metal occurs
When light falls on the complex compound, a part of the with filled orbital of carbonyl group.
electromagnetic wave is absorbed by the electrons of eg or
The next overlap is between filled d – orbital of metal with
t2g sets of orbitals. The rest of the waves are released which
empty anti - bonding orbital of carbonyl group called as
causes colour in the complex compounds. metal – carbonyl back – bonding.
❑ METAL CARBONYLS:

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