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Chapter-9
Coordination Compounds
Coordination Chemistry:
The branch of chemistry which deals with the study of coordination compounds is known as
coordination chemistry.
Addition compounds: -
When two or more than two independently exist compounds are combined in stochiometric ratio
then the compounds formed are known as addition compounds.
It is of two types:
1.Double salt
2. Complex salt
Difference b/wdouble & complex salt: -
Double salt Complex salt
1. The compounds which have existence 1. The compounds which have existence
only in solid state and when it dissolved in solid state as well as in liquid state
into water, it dissociates into ions are (aqueous soln.) are known as complex
known as double salt. salt.
2. All the ions are tested by reagents. 2. All the ions are not tested by reagents.
3. The physical & chemical properties 3. The physical g chemical properties of
of compound are similar from their compound are different from their
constituents. constituents:
4. In these compounds, ionic bond is 4. In these compounds, ionic as well as
present. coordinate is present.
5. Ex: Mohr’s salt 5. Ex:
FeSO4. (NH4)2SO4. 6H2O [Cu(NH3)4] SO4, K4[Fe(CN)6]
Alum –
K2SO4. Al2(SO4)3. 24H2O

Types of complex salt: -

Complex salts are of two types:
1. Cationic complex- In this complex, the coordination sphere has + ve charge.
For ex,
[Cu(NH3)4] SO4, [Ag(NH3)2] Cl, etc.
2. Anionic complex - In this complex, the coordination sphere has -ve charge.
For ex,
K4[Fe(CN)6], K2[HgI4], etc.
Coordination entity: -
A coordination entity consist of a central atom which is bonded to fix no. of ligands.
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Central Atom / ion: -

In a coordination entity, the atom / ion to which a fixed no. of ligands are bonded in a definite
geometrical arrangement is called central atom / ion.
For ex, In complex ion K4[Fe(CN)6], the central atom is Fe.
Ligands:
The atom, molecule or ion which donate a pair of e- to the central atom is known as ligands and the
no. of ligating atoms present in molecule is called denticity.
For ex,
In oxalate ion (C2O4-2) the denticity is 2

COO–

COO-
In EDTA, denticity is 6
Types of ligands:-
1. Monodentate ligand:- It contain one donor atom with a pair of e–
For ex- NH3, H2O, Cl-, F-, etc
2. Bidentate ligand: -It contain two donor atoms.
For ex,
oxalate ion COO–, en (ethane–l, 2–diamine)
COO– CH2 – ׁṄH2
CH2 – ṄH2
*3.Polydentate or hexadentate ligand: -It contain more than two donor atom.
For ex,EDTA (Ethylene diamine tetra acetate)
CH2COO–
CH2 – Ṅ
CH2COO–
CH2COO–
CH2 – Ṅ
CH2COO–
*4. Ambidentate ligand: The ligand which has two donor atom but only one of them form a
coordinate bond at that time with central atom is known as ambidentate ligand. For ex,
(i) M← CN , M ← NC
Cyano / cyanido Isocyano /isocyanido
(ii) M← NO2 M← ONO
Nitro Nitrito
(iii) M← SCN M ← NCS
Thiocyanato Isothiocyanato
*5. Chelating ligand:- When a multidentate ligand can simultaneously coordinate to a metal
ion by more than one donor atom then a ring like structure is formed. This structure is known
as chelating and ligand is knowna chelating.
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For ex,
[Cu (en)2]+2

CH2 – H2Ṅ ṄH2– CH2]+2

Cu
CH2 – H2Ṅ ṄH2– CH2

# Characteristics of chelating ligands:-

*1. They form stable complexs.
2.They do not contain double bond
3. Ligands with larger group forms unstable complexes than the ligands with smaller group.
Coordination Number: -
The total no. of e– pairs which is donated by ligand to central atom is known as coordination
number.
For ex,
In K4[Fe(CN)6], coordination no. is 6 and in [Cu(en)2]+2, coordination no is 4.
Oxidation Number:
It is defined as the no representing the charge on the central metal atom or ion initially they have
before the combining with ligands.
For ex,
(i) K4[Fe(CN)6]
O.N of Fe = +1x 4+ 𝜘 -1x6 = 0
4+𝜘-6=0
𝜘 = +2
(ii) [Cu(NH3)4]SO4
O.N of Cu =𝜘 + 0 x 4 – 2=0
𝜘–2=0
𝜘 = +2
Homoleptic complex: -
The complex in which central metal atom is bonded with only one type of ligand is known as
homoleptic complex.
Forex,
K4 [Fe(CN)6], K2[HgI4]

Heteroleptic complex: -
The complex in which central metal atom is bonded with more than one type of ligand is known as
heteroleptic ligand.
For ex,
[Pt (NH3)2 Cl2]+, [Cr(H2O)4Cl2]+
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Effective Atomic No. (EAN): -

The total no of e- possessed by the central metal ion in the complex including those e- donated by
ligands is called EAN.
EAN = atomic no. of metal - O.N + e-gained from ligands.
Forex,
(i) K4 [Fe(CN)6]
EAN of Fe = 26-2+12
= 36
(ii) [Cu(NH3)4] SO4
EAN of cu=29-2 +8
=35
IUPAC and common name of ligands
Symbol Common Name IUPAC Name
-
CN cyanide cyano / cyanido
-
NC isocyanide Isocyano /isocyanido
-
SCN Thiocyanate Thiocyanato
NCS- Isothiocyanate Isothiocyanato
NO2- nitro Nitrito -N
ONO- nitrite Nitrito -O
N-3 nitride nitrido
P-3 phosphide phosphido
-
F Fluoride fluorido
-
Cl chloride chlorido
-
Br Bromide Bromido
-
I Iodide Iodido
H- Hydride Hydrido
OH- Hydroxide Hydroxido
NH2- amide amido
NH-2 imide imido
ClO4- Perchlorate Perchlorato
-2
O oxide Oxo
-2
O2 Peroxide Peroxo
-2
CO3 carbonate carbonato
-
CH3COO acetate acetato
NO3- nitrate nitrato
S-2 sulphide suphido
SO4-2 sulphate sulphato
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SO3-2 sulphite sulphito

S2O3-2 thiosulphate thiosulphato
C2O4-2 (ox) oxalate oxalato
NH3 ammonia ammine
H2 O water / hydrate aqua / aquo
CO carbon monoxide carbonyl
NO Nitric oxide Nitrosyl
PH3 Phosphine phosphine
(C6H5)3P triphenyl phosphine triphenyl phosphine
C6H6 Benzene Benzene
C6H5 Phenyl Phenyl
CH2 – NH2 ethylene diamine ethane-1,2-diamine
(en)
CH2 – NH2
dmg-1 dimethylglyoxime dimethylglyoximato
-4
EDTA Ethylene diaminetetra Ethylene diamine
acetate tetraacetato

Latin Name of Metals:-

Metal Symbol Latin Name
Sodium Na Natrium
Potassium K Kalium
Iron Fe Ferrum
Silver Ag Argentum
Copper Cu Cuprum
Gold Au Aurum
Tin Sn Stannum
Lead Pb Plumbum
Antimony Sb Stibium
Tungsten W wolfrum
Mercury Hg Hydragyrum
Werner's Coordination Theory: -
1. All metals in coordinate compound exhibit two types of valency.
(i) Primary valency or ionisable valency or oxidation no
(ii) Secondary valency or non-ionisable valency or coordination no.
2. The metal atom satisfy its both valency.
3. Primary valency is satisfy by -ve ions and it is represented by dotted line.
4. Secondary valency is represented by arrow and it give definite geometry to coordinate
compound.
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For ex; the coordinate compound having 4 coordination no has square planar or tetrahedral
geometry while the compound having coordination no. 6 has octahedral geometry.
* [CO(NH3)6 ]Cl3

* This compound on reaction with AgNO3 give 3 moles ofAgCl in the form of ppt .
Valence Bond Theory (VBT): -
The basic principle of this theory are following –
1. Orbital hybridisation.
2. Bonding b/w ligands & metal ion.
3. Relationship b/w the observed magnetic property and type of bond.
* Spectrochemical series - The arrangement of various ligands in increasing order of their field
strength is known as spectrochemical series.
I- < Br – < S2- < SCN- < Cl- < F- < ONO- < OH- < SO4-2 < C2O4-2 < O-2 < H2O < NCS- < EDTA-4 < NH3
< py < en < phen < NO2- < CH3 < CN- < CO
From I- to H2O are weak field ligands and from NCS- to CO are strong field ligands.
Ex-1 [Ni (CN)4]2-
8 2
28Ni = 3d 4s
+2 8
26Ni = 3d 4s°

↿⇂ ↿⇂ ↿⇂ ↿ ↿

CN is a strong ligand.
[Ni(CN)4]-2 = ↿⇂ ↿⇂ ↿⇂ ↿⇂ xx xx xx xx

dsp2
Hybridisation- dsp2
Geometry – square planar
Nature- diamagnetic
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Ex-2 [NiCl4]2-
8 2
28Ni = 3d 4s
+2 8
26Ni = 3d 4s°

↿⇂ ↿⇂ ↿⇂ ↿ ↿

Cl is a weak ligand.
[NiCl4]-2 = ↿⇂ ↿⇂ ↿⇂ ↿ ↿ xx xx xx xx

xx
sp3
Hybridisation- sp3
Geometry – Tetrahedral
Nature- paramagnetic

μ = 𝑛(𝑛 + 2) = 2(2 + 2) = 8 = 2.83

Where n is unpaired e-

Ex-3 [Fe(CN)6 - 4
26Fe = 3d6 4s2
+2
24Fe =3d6 4so

= ↿⇂ ↿ ↿ ↿ ↿
CN is a strong ligand.
[Fe(CN)6]-4 = ↿⇂ ↿⇂ ↿⇂ xx xx xx xx xx xx

d2sp3
Hybridisation- d2sp3
Geometry – Octahedral / Inner
Nature- diamagnetic
Limitations of VBT: -
1. It does not give any idea about colour of coordination compounds.
2. It involves a no. of assumptions.
3. It does not distinguish b/w strong & weak ligands.
4. It does not explain the stability of coordinate compounds.
Crystal Field Theory (CFT): -
1. According to this theory, the bonding b/w the central metal ion and ligand is electrostatic.
2. Ligands are considered as point charges.
3. The five d-orbitals in an isolated gaseous metal atom are degenerate orbitals. But in
coordinate complexes, due to a symmetrical negative field of ligand, the d-orbital split into
two sets of orbitals.
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4. The 3-d orbitals have low energy and are known as t2g orbitals and two orbitals have higher
energy and are known as eg orbitals.
5. The splitting of degenerate orbital due to presence of ligand in definite geometry is known as
crystal field splitting and the difference of energy b/w two sets of orbitals is known as crystal
field stabilization energy (CFSE).It is denoted by ∆o.
# Crystal field splitting in octahedral complexes–
In octahedral complexes, the d-orbital splits into 3 orbitals of lower energy t2g and two
orbital of higher energy eg. the energy of 2eg-orbital will increase by 3/5∆o and the t2g
orbital will decrease by 2/5∆o

# Crystal field splitting in tetrahedral complexes -

The crystal field splitting energy for ∆o and ∆t complexes is related as

∆t = 4/9 ∆o
Colour in coordination compounds -
The crystal field theory attributes the colour of compounds by d-d transition of e- jumped from t2g to
eg orbital in octahedral complex. In the absence of ligand, the crystal field splitting does not take
place. Hence, the substance is colourless.
For ex- anhydrous CuSO4 is colourless but CuSO4 .5H2O is coloured (blue colour).
Isomerism:
Compounds having same molecular formula but different structural formula are known as isomers
and phenomenon is known as isomerism.
It is of two types: -
(1.) Structural isomerism-These isomers have different ligand with in the coordination
sphere. It is again of following types.
(i) Ionisation Isomerism - This isomerism arises due to exchange of ions inside and outside
the coordination sphere.
For ex- [Co(NH3)5 Cl] SO4 and [CO(NH3)5 SO4] Cl
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(ii) Hydrate or solvate isomerism - This isomerism arises due to differ in water molecule
present as ligand.
Ex;
[Cr(H2O)6] Cl3, [Cr(H2O)5 Cl] H2O.Cl2,
[Cr(H2O)4 C12] (H2O)2 Cl and [Cr(H2O)3 Cl3](H2O)3
(iii) Linkage isomerism- This isomerism arises when more than one atom in
monodentate ligand may function as donor atom.
For ex - [Cr(H2O)SCN]+2& [Cr(H2O)5 NCS]+2
(iv) Coordination isomerism - This isomerism is shown by those compounds in which both
cation and anion are complex ion.
For ex- [Co(NH3)6] [Cr(CN)6] or [Cr (NH3)6 ] [Co (CN)6]
(2.) Stereo isomerism - The compound which contain same ligands in their coordination
sphere but differ in the way in which these ligands are arranged in the space are known as
stereo isomers. and the phenomenon is known as stereo isomerism. It is of two types:
(i) Geometrical - It is also known as cis- trans isomerism. This isomerism is due to the
ligand occupying the position around the central atom.
The isomers in which similar ligands occupying adjacent positions is known as cis isomers
and isomers in which similar ligands occupying opposite position is known as trans isomers.

# Square planar complexes

(I) MA2 B2 type[Pt(NH3)2 C12]

Cl NH3 Cl NH3
Pt Pt
Cl NH3 H3 N Cl
(Cis) (trans)

(II) MA2 BC type [Pt (NH3)2 Cl NO2]

NH3 Cl NH3 Cl
Pt Pt
NH3 NO2 O2 N NH3
(Cis) (trans)

(III) MABCD type

In this type, the position of one ligand is fixed and remaining 3 ligands are placed in trans
position one by one.

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

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H3N Py]+ H3N H2O]+

(cis) Pt or Pt or
O2 N H2 O O2 N Py (trans)

H3N H2O]+
Pt
Py NO2 (trans)

#Octahedral complexes
(I) M A4 B2 type [ CO(NH3)4 Cl2] +

(II) M(AA)2 B2 type [ Co(en)2Cl2 ]+

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# Facial and Meridiagonal geometrical Isomers

Octahedral complexes of the type MA3B3 also exhibit geometrical isomerism.
When three ligands with donor atom are on same triangular face of octahedral then it is known as
facial or fac isomers and if these ligands are on the same equatorial plane of the octahedron, then
this is shown as meridional ormerisomer.
For ex;
Cl NH3
H3 N Cl Cl Cl
CO Co
H3 N Cl NH3 Cl
NH3 NH3
Fac-isomer mer-isomer
(ii) Optical isomerism -The compounds which rotate the plane polarised light are known as
optically active compounds and the phenomenon is known as Optical isomerism.
Optical isomers are mirror image cannot be superimposable on one another. Thus these are also
called enantiomers. The molecule is also called chiral. The two forms are called dextro& laevo
rotatory depending upon the direction they notate the plane polarised light. It is common in
octahedral complex.
(I) MA2B2C2 type [Pt(NH3)2 Cl2 (Py)2]+2
NH3 +2 NH3 +2
Py NH3 H3 N Py
Pt Pt
Py Cl Cl Py
Cl Cl
(Cis)
NH3 +2 NH3 +2
Cl Py Py Cl
Pt Pt
Py Cl Cl Py
NH3 NH3
(trans)
(II) M(AA)2 B2 type [Co(en)2Cl2]+
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No isomers

(III) M (AA)2 BC type [Co(en)2NH3 Cl]+

(IV) M(AA)3 type - [Co(en)3]+3

Stability of coordinate compounds

The stability depends upon following factors:
1. The nature of central atom - Greater the charge density of central atom, greater is the
stability of complexes for ex- the complexes of Fe+3 are more stable than Fe+2 ion.
2. Nature of ligand- The more basic ligand have a tendency to donate a pair of e- to central
metal atom is more and hence, the resulting complex is very stable for ex- the complex having
F- ion are more stable than the complexes having Cl- or Br- ion.
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3. Chelate effect - When chelation occurs, the stability increases.Thus, [Cu (en)2]+2is more stable
than [CuCl4]-2
Bonding in metal carbonyl
The metal carbon bonds in metal carbonyl have both sigma & pie character.The metal carbon σ
bond is formed by the donation of lone pair of e- from the carbonyl carbon to the vacant d-orbital of
metal. This is actually coordinate bond (C→M). Thus, CO acts as a ligand and c act as donor atom.
The metal carbon π bond is formed by donation of a pair of e- from filled d-orbital of metal into the
vacant anti bonding xa molecular orbital of carbon monoxide.Thus, M-C bond in metal carbonyl
consist of weak (C→ M) bond which is σ and (M→ C) π a bond which result due to back bonding.
This back bonding create synergic effect which strengthens the bond b/w CO and metal and stabilise
it. For ex- [Ni(CO4], [Fe(CO)5], [Cr(CO)6]
Application of coordinate compounds
1. In metallurgy: - The extraction of several metals from their ores involves complex
formation for ex- silver & gold can be extracted from there ores by cyanide complex
formation.
4Au + 8KCN + 3H2O + O2 → 4K[Au(CN)2] + 4 KOH
2K[Au(CN)2] + Zn → K2[Zn (CN]4] + 2Au
* Ni is purified by Mond process. In this process, the impure Ni is converted into complex
compound [Ni(CO)4] which decompose on heating to give pure nickel.

Ni + 4CO → (Ni(CO)4] ∆ Ni + 4CO

(impure) (pure)
2. In qualitative analysis: -
(i) In detection of Cu+2– Cu+2 ion is detected by formation of dark blue colour solution
of tetra amine copper (II) ion.
Cu+2 + 4NH3→ [ Cu(NH3)4]+2
(dark blue)
(ii) In detection of Ni+2– Ni+2is detected by the formationof cherry red complex with
dmg.
NiCl2 + 2dmg + 2NH4OH → [Ni(dmg)2] + 2NH4Cl + 2H2O
(cherry red)
3. Quantitative analysis: EDTA is used in the determinationof several metal ions such as Cu+2,
Zn+2 +Fe+2, CO+2, Ni+2 etc.
4. In medicinal chemistry:- The cis platin [Pt (NH3)2Cl2] is used in the cancer treatment as
carcinogen . EDTA complex of Ca is used in the treatment of lead poisoning.
5. In biological System: -
(i) Haemoglobin, a complex of ion is used as a oxygen carrier in human body.
(ii) Chlorophyll, a complex of Mg is used in photosynthesis.
(iii) Vitamin B-12 is a complex of Co is used in treatment of pernicious anaemia.
6. In estimation of hardness of Water:- EDTA is used in the estimation of presence of Ca+2
and Mg+2 ion in hard water.
7. In photography: - In black & white photography, AgBr combine with hypo
solution(Na2S2O3) to form complexion. [Ag(S2O3)]-2.