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128 | Chemistry-XII
UNIT 8
Coordination Compounds
1. Introduction
Complex compounds or coordination compounds are those molecular compounds
which retain their identity in solid as well as in solution are known as complex
compounds.
Example,
K4 [Fe(CN)6] + H2O → 4K(aq)+ + [Fe(CN)6]4−(aq)
2. Types of Complex
(i) Anionic complex
K3[Fe(C2O4)3] → 3K+ + [Fe(C2O4)3]3−
anionic complex
(ii) Cationic complex
[CoCl2(en)2]Cl → [CoCl2(en)2]+ + Cl−
cationic complex
(iii) Neutral complex
[Ni(CO)4]
neutral complex
3. Ligands
The ions or molecules bound to the central atom/ion in the coordination entity are
called ligands.
Types of Ligands
(i) Unidentate, a ligand which is bound to a metal ion through a single donor atom.
e.g., H2O, NH3, CO, Cl−, NH2− etc.
(ii) Didentate, a ligand which is bound to a metal ion through a two donor atoms.
e.g.,
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The d- and f-Block Elements | 129
(iii) Polydentate, a ligand which is bound to a metal ion through a several donor
atoms.
e.g., ethylene diamine tetraacetate ion [EDTA]4−.
(iv) Ambidentate ligands, which can ligate through two different atoms.
e.g., − NO2 – ONO, – SCN – NCS etc.
(v) Chelate ligands, these may be a di- or polydentate ligand which form closed
ring with central metal ion. Closed ring is known as chelate ring. Number of more
chelate ring in complex, complex will be more stable. The number of such ligating
groups is called the denticity.
4. Homoleptic and Heteroleptic Complexes
Complexes in which a metal is bound to only one kind of donor groups e.g.,
Co(NH3)6]3+ are known as homoleptic. Complexes in which a metal is bound to more
than one kind of donor groups e.g., [Co(NH3)4Cl2]+, are known as heteroleptic.
5. Nomenclature of Coordination Compounds
Cationic Complex
[Cr(NH3)3(H2O)3]Cl2
triamminetriaquachromium (III) chloride
(i) Prefixes mono, di, tri, etc. are used to indicate the number of the individual
ligands and ligands are named in an alphabetical order.
(ii) Central metal atom and oxidation state indicated by Roman numeral in
parenthesis.
(iii) Name of ionisable anion.
Anionic Complex
K3[Fe(CN)6]
Potassium hexacyanoferrate (III)
(i) Name of ionisable metal and oxidation state
(ii) Name of ligand in an alphabetical order
(iii) Central metal atom + ate and oxidation state
Neutral Complex
[Pt(NH3)2Cl(NO2)]
Diammine chloronitrito-N-platinum (II)
(i) Name of ligands in an alphabetical order
(ii) Central metal atom and oxidation state
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130 | Chemistry-XII
All electrons are paired therefore, complex will be diamagnetic in nature.
e.g., Outer orbital complex, [CoF6]3−
Complex has unpaired electrons, therefore, complex will be paramagnetic in nature.
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The d- and f-Block Elements | 133
3+
Orbitals of Co ion
3d 4s 4p
3d 4s 4p
–
[CoCl4]
× × × ×
4s 4p
Four pairs of
electrons from 4Cl
Complex has unpaired electrons. Complex will be paramagnetic in nature.
Crystal Field Theory
The five d-orbitals are split into lower and higher energy level due to approach of
ligands is known as crystal field theory. The five d-orbitals in a gaseous metal atom/ion
have same energy.
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134 | Chemistry-XII
t23g e1g . Ligands for which ∆o < p are known as weak field ligands and form high spin
complexes.
• If ∆o > p, it becomes more energetically favourable for the fourth electron to
occupy a t2g orbital with configuration t24g eg . Ligands which produce this effect are
known as strong field ligands and form low spin complexes, where p represents the
energy required for electron pairing in a single orbital.
(ii) Crystal field splitting in tetrahedral coordination entities.
d xy, dxy, d yz
Energy t2g
Bary 2/5
centre t
Average energy
of the d-orbitals in 3/5
spherical crystal field
eg
{ { d x – y , dz
2 2 2
• Due to less crystal field stabilization energy, it is not possible to pair electrons
and so all the tetrahedral complexes are high spin.
8. Colour in Coordination Compounds
• In complex compounds d-orbitals split in two sets t2g and eg. These have different
energies. The difference in energies lies in visible region and electron jump from ground
state t2g level to higher state eg level. This is known as d-d transition and it is responsible
for colour of coordination compounds.
• d-d transition takes place in d1 to d9 ions, so the ions having d1 to d9 configuration
are coloured. On the other hand, the ions d0 and d10 configuration do not show d-d
transition.
9. Importance and Applications of Coordination Compounds
• Hardness of water is estimated by simple titration with Na2EDTA. The Ca2+ and
Mg2+ ions form stable complexes with EDTA.
• Some important extraction processes of metals, like those of silver and gold
make use of complex formation.
• Similarly, purification of metals can be achieved through formation and
subsequent decomposition of their coordination compounds. For example, impure
nickel is converted to [Ni(CO)4], which is decomposed to yield pure nickel.
• Coordination compounds are used as catalysts for many industrial processes.
Examples include rhodium complex, [(Ph3P)3RhCl], a Wilkinson catalyst, is used for
the hydrogenation of alkenes.
Supplementary List of Ligands
Ligand F− Cl− Br− I− OH− CN− O2− O22− O 2− CO32− PH3
Name fluoro chloro bromo iodo hy- cyano oxo per- super-oxo car-bon- phos-
droxo oxo ato phine
Ligand SO42− NO2− ONO− SCN−1 NCS CH3COO− C5H5N S2− S2O32− NO3− SO32−
Name sulpha- nitro nitrito thiocy- iso- acetate pyridine sul- thiosul- nitrato sulphi-
to anato thio- (Py) phido phato to
cyana-
to
Ligand NC− (C6H5)3P CS NH2− NH2− H2NCSNH2 C2O42− H2O NH3 CO NO
Name isocy- triphenyl thio- amido imido thiourea oxalate aqua ammine carbo- nitro-
ano phos- carbo- (tu) (ox) nyl syl
phine nyl
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136 | Chemistry-XII
ANSWERS
1. (b) 2. (c) 3. (b) 4. (a) 5. (c) 6. (a) 7. (c) 8. (a) 9. (d) 10. (b)
11. (b) 12. (c) 13. (a, c) 14. (a, c) 15. (a, c) 16. (b)
17. (d) 18. (a) 19. (d) 20. 6
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The d- and f-Block Elements | 139
(ii) µ BH= n ( n + 2=
) 0
n = 5, So =µ n ( n + 2)
=µ 5 (5 + 2)
µ = 35 = 5.96 BM
Q. 2. Explain the following :
(i) NH3 act as a ligand but NH4+ does not.
(ii) CN− is a ambidentate ligand.
Ans. (i) NH3 has one lone pair while NH4+ does not.
(ii) Because it has two donor atoms in a monodentate ligand.
Q. 3. Mention the main postulates of Werner theory.
Ans. (i) Metal ion has two types of valency.
(ii) Primary valency and secondary valency.
(iii) Secondary valency is equal to coordination number.
Q. 4. Draw the structure of :
(i) [Ni(CO)4] (ii) [Fe(H2O)6]+3
Ans.
d2sp3
(ii)
(iii) [M(AA)3] type complex show optical isomerism.
t2g4 eg0
(iv)
Q. 2. (i) Discuss the nature of bonding in metal carbonyls.
(ii) Draw figure to show the splitting of d-orbitals in an octahedral crystal
field and write electronic configuration of M2+ ion when :
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144 | Chemistry-XII
p > ∆o
(a)
∆o > p
(b)
Ans. (i) The metal carbon bond in metal carbonyls possess both σ and π character.
The M – C σ bond if formed by the M ← C ≡ O while M – C π bond if
formed by the donation of a pair of electron from filled d-orbital of metal to
antibonding π* orbital of CO.
(ii)
Source: EDUDEL