CHAPTER-9 COORDINATION COMPOUND

Intoduction Simple Salt:- A salt is formed by the neutralisation of an acid by a base.It give one type of anion
andcation.Example KCl,NaCl
Double Salt:-A salt that contains more than one cation or more than one anion. It is obtained by
combination of two different salts Example.K2SO4.Al2SO4.24H2O, carnallite, KCl.MgCl2⋅6H2O
Complex Salt:-A salt which ionized form complex ion. In these salt, Ion or Molecule are joined by
coordination bond with metal. These are also called coordination compound
Coordination Coordination compounds are chemical compounds that consist of an anions or neutral molecules that are
Compound bound to a central atom with coordinate covalent bonds.
Diffrance SN Double Slat Complex Salt
Between 1 They do not have coordination bond They have coordination bond
duouble salt 2 They exist in solid state They exist in solid as well as in aqueous solution
and complex 3 They lose their identity in aqueous They do not lose their identity in aqueous solution
salt solution
4 They contain two salt in equimolar ratio They contain ions which may or may not be in
equimolar ratio
5 Metal shows one type of valancy Metal shows two type of valancy
Complex salt 1 mol CoCl3.6NH3 (Yellow) gave 3 mol AgCl

1 mol CoCl3.5NH3 (Purple) gave 2 mol AgCl

1 mol CoCl3.4NH3 (Green) gave 1 mol AgCl

Types of Anionic complex K3 [Fe(C2O4)3]  3K+ + [Fe(C2O4)3]3 anionic complex

complex Cationic complex [CoCl2 (en)2 ]Cl  [CoCl2 (en)2 ]+ + Cl cationic complex
Neutral complex [Ni(CO)4 ] neutral complex
Term

Warner 1. In coordination compounds metals show two types of linkages (valences)-primary and secondary.
Theory 2. The primary valences are normally ionisable and are satisfied by negative ions.
3. The secondary valences are non ionisable. These are satisfied by neutral molecules or negative ions.
The secondary valence is equal to the coordination number and is fixed for a metal.
4. The ions/groups bound by the secondary linkages to the metal have characteristic spatial
arrangements corresponding to different coordination numbers.
Element Sc Ti V Cr Mn Fe Co Ni/Pt/Pd Cu Zn/Cd/Hg
CN 6 6 6 6 6 6 4/6 4 4

OS +3 +2/+3 +2 +2/+3 +2/+3 +2 +2 +2

IMPORTAN Coordination Entity:-
T TERMS A chemical compound in which the central ion or atom (or the coordination centre) is bound to a set
number of atoms, molecules, or ions is called a coordination entity.For example [CoCl3(NH3)3], and
[Fe(CN)6]4-.
Ligands:-The atoms, molecules, or ions that are bound to the coordination centre or the central atom/ion are
referred to as ligands.

Coordination Number
The total number of sigma bonds through which the ligands are bound to the coordination centre.
[Ni(NH3)4]2+, the coordination number of nickel is 4.

Coordination Sphere
The central atom/ion and the ligands attached to it are enclosed in square bracket and is collectively termed
as the coordination sphere. The ionisable groups are written outside the bracket and are called counter ions.
For example, in the complex K4[Fe(CN)6], the coordination sphere is [Fe(CN)6]4-

Coordination Polyhedron
The spatial arrangement of the ligand atoms which are directly attached to the central atom/ion
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Homoleptic:-Coordination compound having same ligand attatched to central atom called Homolyptic
complex. [Co(NH3)6]3+
Heteroleptic Complex :-Coordination compound having different ligand attached to central atom called
Heteroleptic complex. [Co(NH3)4Cl2]+
Ligand The ions or molecules bound to the central atom/ion in the coordination entity are called ligands.
Unidentate:- When a ligand is bound to a metal ion through a single donor atom for example
NH3,H2O
Didantate:- When a ligand bind through two donor atoms with central atom or ion
For example H2NCH2CH2NH2 (ethane-1,2-diamine) or C2O42– (oxalate)
Polydentate:- when several donor atoms are present in a single ligand for example (EDTA4-)

Ambidentate ligand:- Ligand which has two different donor atoms but attached with either of the two
doner atom with central metal atom/ion

LIST OF Anion Ligand

LIGAND Molecular
Ligand Name Molecular Formula Ligand Name
Formula
F- Fluoro/Flurido OH -
Hydroxo
Cl- Chloro/Chlorido SO42- Sulfato
Br- Bromo/bromido S2O32- Thiosulfato
I- Iodo/Iodido NO2- Nitrito-N-; Nitro
O2- Oxo ONO- Nitrito-O-; Nitrito
CN- Cyano/Cyanato SCN- Thiocyanato-S-; Thiocyanato
NCS- Thiocyanato-N
Neutral Ligands
Molecular Formula of Ligand Ligand Name
NH3 Ammine
H2O Aqua
CO Carbonyl
NO Nitrosyl
CH3NH2 Methylamine
C5H5N Pyridine
Polydentate ligand
Short name Extended name
en Ethylenediamine/ethane1,2diamine
ox2- Oxalato
EDTA4- Ethylenediaminetetraacetato
IUPAC Monodentate
Number of Ligands Polydentate Ligands
NAME Ligands
1 mono -
2 di bis
3 tri tris
4 tetra tetrakis
5 penta pentakis
Name of English Latin Anion name Latin name Anion name Anion name
metal
name name
Copper Cuprum Cuprate Chromium chromium Chromate

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Platinum Platinum Platinate Gold Aurum Aurate
Palladium Palladium Palladate Mercury Hydragyrum hydrogenate

Lead Plumbum plumbate Nickel Nickel Nickelate

Silver Argentum Argentate Iron Ferrum Ferrate
Tin Stannum Stannate Zinc Zinc Zincate
IUPAC SN Complex Compound Name
Nomenclatur 1 [Co(NH3)4(H2O)Cl]Cl2 Tetraamineaquachloridocobalt(III) chloride
e 2 K3[Al(C2O4)3] Potassium trioxalatoaluminate(III)
+
3 [CoCl2 (en)2 ] Dichloridobis(ethane-1,2-diamine)cobalt(III)
4 [Pt(NH3)2Cl(NO2)] Diamminechloridonitrito-N-platinum(II)
5 Hg[Co(SCN)4] Mercury tetrathiocyanatocobaltate(III)
6 [Co(NH3)5(CO3)]Cl Pentaamminecarbonatocobalt(III) chloride
7 [Co(H2NCH2CH2NH2)3]2(SO4)3 tris(ethane-1,2–diammine)cobalt(III) sulphate
8 [Ag(NH3)2][Ag(CN)2] diamminesilver(I) dicyanoargentate(I)
Isomerism Linkage Ionisation Solvate Coordination
in Coordination Coordination Coordination Coordination
Coordination compound having compound having compound having compound having
Compounds same molecular same molecular same molecular same molecular
formula but differ in formula but differ in formula but differ in formula but differ in
the linkage of donar the ionisation of the solvate/Water the coordnation
atom of ligand attatch coordination molecule act as ligand entities of
with central metal compound [Cr(H2O)6]Cl3 (violet) coordiantion
atom.NO2/ ONO, [Co(NH3)5(SO4)]Br [Cr(H2O)5Cl]Cl2.H2O compound
CN/NC, SCN/NCS [Co(NH3)5Br]SO4. (grey-green) [Cr(NH3)6][Co(CN)6]
[Co(NH3)5(NO2)]Cl2 [Co(NH3)6][Cr(CN)6]
[Co(NH3)5(ONO)]Cl2
Stereoisomer Coordination compound having the same chemical formula and chemical bonds but differ in the spatial
ism arrangement of atom or molecule around the central metal atom
Geometrical
Coordination compound having the same Geometrical isomer of [MX4L2] molecule
chemical formula and chemical bonds but
differ in the geometrical arrangement of atom
or molecule around the central metal atom
Geometrical isomer of [MX2L2] molecule
Cis Isomer:-Having same ligand at same side
Trans Isomer:- Having same ligand at opposit
side

Gometrical Geometrical isomer of [MX2(L–L)2] Geometrical isomer [Ma3b3] like

isomer [Co(NH3)3(NO2)3]

Note:-Tetrahedral complexes do not show geometrical isomerism because the relative positions
of the unidentate ligands attached to the central metal atom are the same with respect to each
other.
Optical Coordination compound having the same
chemical formula and chemical bonds but
differ in the specific rotation of plane
polarise light
d isomer:-Optical isomer which rotate
plane polarise light in right hand direction
l isomer:- Optical isomer which rotate
plane polarise light in left hand direction
Practice

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Draw structures of geometrical isomers of
[Fe(NH3)2(CN)4]–
Out of the following two coordination
entities which is chiral (optically active)?
(a) Cis-[CrCl2(ox)2]3– (b) trans-
[CrCl2(ox)2] 3–

Valence According to this theory, the metal atom or ion under the influence of ligands can use its (n-1)d, ns, np or
Bond ns, np, nd orbitals for hybridisation to yield a set of equivalent orbitals of definite geometry such as
Theory octahedral, tetrahedral, square planar.

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Limitations (i) It involves a number of assumptions.
of Valence (ii) It does not give quantitative interpretation of magnetic data.
Bond (iii) It does not explain the colour exhibited by coordination compounds.
Theory (iv) It does not give a quantitative interpretation of the thermodynamic
or kinetic stabilities of coordination compounds.
(v) It does not make exact predictions regarding the tetrahedral and
square planar structures of 4-coordinate complexes.
(vi) It does not distinguish between weak and strong ligands
VBT
Example

[Co(NH3)6]3+

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[Ni(CN)4]2-

Inner orbital Inner Orbital Complex :-Complex which are formed due to participation of (n -1)d orbital’s.Central atom
complexes is d2sp3 hybridise and shape of complex will be octahedral.
and Outer Outer Orbital ComplexComplex:- Complex which are formed due to participation of (n -1)d
Orbital orbital’s.Central atom is sp3d2 hybridise and shape of complex will be octahedral .Generally halides (F ,
Complex Cl , Br , I ), SCN , S2 form outer orbital complexes and other ligands form inner orbital complexes.

CFT 1. The crystal field theory (CFT) is an electrostatic

model
2.It consider the metal-ligand bond to be ionic arising
purely from electrostatic interactions between the metal
ion and the ligand
3. Ligands are treated as point charges in case of anions
or point dipoles in case of neutral
molecules.
4. The five d orbitals in an isolated gaseous metal
atom/ion have same energy, i.e., they are degenerate
5.When ligand approaches to central metal ion/complex
then these d orbital does not remain with same energy
and split into two type of orbital called t2g and eg orbital.
6.Splitting of d sub shell in octahedral complex and
Tetrahedral complex

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spectrochemi Arrangement of Ligand in the increasing order of their CFSE value is called Specrtrochemical series.
cal series

CFSE The energy gap between t2g and eg orbital is called CFSE
(Crystal field Factor Affecting CFSE Value:-
stabilisation 1. Oxidation state of the metal ion:- The
energy) magnitude of increases with increasing ionic
charge on the central metal ion.
2. Nature of the metal ion:- Significant
differences in also occur for analogous
complexes within a given group,
the trend being 3d > 4d > 5d.
3. Number and geometry of the ligands:- The 4.Nature of the ligands:- The magnitude of varies
crystal field splitting in a tetrahedral field is from strong to weak ligands. Strong ligands are
smaller than that in those which exert a strong field on the central
an octahedral field. For the same metal ion, metal ion and hence have higher splitting power
ligands and metal-ligand distances,
( Δt = 4/9 Δo.)

Colour in It is due to d-d transition

Coordination
Compounds

Bonding in  The metal-carbon bond in metal carbonyls

metal possess both σ and π character.
Carbonyl  The M–C σ bond is formed by the donation of lone pair of
electrons on the carbonyl carbon into a vacant orbital of the
metal.
 The M–C π bond is formed by the donation of a pair of
electrons from a filled d orbital of metal into the vacant
antibonding π* orbital of carbon monoxide.
 The metal to ligand bonding creates a synergic effect which
strengthens the bond between CO and the metal
Importance  These are useful in many qualitative and quantitative chemical analysis. For Example EDTA, DMG
and (dimethylglyoxime), α–nitroso–β–naphthol, cupron, etc.
Applications  Hardness of water is estimated by simple titration with Na2EDTA. The Ca2+ and Mg+2 ions form stable
of complexes with EDTA.
Coordination  In metallurgical process like extraction of gold,siliver and Nickel
Compounds  In Biolgical system:-The pigment responsible for photosynthesis, chlorophyll, is a coordination

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compound of magnesium. Haemoglobin, the red pigment of blood which acts as oxygen carrier is a
coordination compound of iron. Vitamin B12, cyanocobalamine, the anti– pernicious anaemia factor, is
a coordination compound of cobalt. Among the other compounds of biological importance with
coordinated metal ions are the enzymes like, carboxypeptidase A and carbonic anhydrase (catalysts of
biological systems).
 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.
 In black and white photography, the developed film is fixed by washing with hypo solution which
dissolves the undecomposed AgBr to form a complex ion, [Ag(S2O3)2]3–
 . Excess of copper and iron are removed by the chelating ligands D–penicillamine and desferrioxime B
via the formation of coordination compounds.
 EDTA is used in the treatment of lead poisoning. Some coordination compounds of platinum effectively
inhibit the growth of tumours. Examples are: cis–platin
Organometal The chemical compounds which contain at least one bond between a metallic element and a carbon atom
ic Compound belonging to an organic molecule.

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