UNIT – 9 – COORDINATION COMPOUNDS

Coordination compounds are those addition molecular compounds which retain their
identity in solid state as well as in dissolved state. In these compounds, the central
metal atom or ion is linked by ions or molecules with coordinate bonds. e.g., Potassium
ferrocyanide, K4 [Fe(CN)6].

Double Salts
These are the addition molecular compounds which are stable in solid state but
dissociate into constituent ions in the solution.
e.g., Mohr’s salt, [FeSO4·(NH4)2SO4.6H2O get dissociated into Fe2+, NH4+ and SO42-
ions.

Terms Related to Coordination Compounds

1. Complex ion or Coordination Entity
It is an electrically charged species in which central metal atom or ion is surrounded by
number of ions or neutral molecules.
(i) Cationic complex entity It is the complex ion which carries positive charge. e.g.,
[Pt(NH3)4]2+
(ii) Anionic complex entity It is the complex ion which carries negative charge. e.g.,
[Fe(CN)6]4-
2. Central Atom or Ion
The atom or ion to which a fixed number of ions or groups are bound is central atom or
ion. It is also referred as Lewis acid. e.g., in (NiCI2(H2O)4]. Ni is central metal atom. It is
generally transition element or inner-transition element.
3. Ligands
An ion or molecule capable of donating a pair of electrons to the central atom by a
coordinate bond is called ligand. It may be neutral, positively or negatively charged.
Example: H2O, CN-, NO+ etc.
 Unidentate ligands: Ligands with only one donor atom, e.g. NH3, Cl-, F- etc.
 Bidentate ligands: Ligands with two donor atoms, e.g. ethylenediamine, C 2O42-
(oxalate ion) etc.
 Tridentate ligands: Ligands which have three donor atoms per ligand, e.g. (dien)
diethyl triamine.
 Hexadentate ligands: Ligands which have six donor atoms per ligand, e.g. EDTA.

Ambidentate ligand:
Ligands which can ligate (link) through two different atoms present in it are called
ambidentate ligand. Example: NO2-,and SCN-. NO2- can link through N as well as O
while SCN- can link through S as well as N atom.

Chelating Ligands:
 Multidentate ligand simultaneously coordinating to a metal ion through
more than one site is called chelating ligand. Example: Ethylenediamine
(NH2CH2CH2NH2)

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 These ligands produce a ring like structure called chelate.
 Chelation increases the stability of complex.
4. Donor atom: An atom of the ligand attached directly to the metal is called the donor
atom. For example: in the complex K4[Fe(CN)6], carbon is a donor atom.
5. Coordination Number
It is defined as the number of coordinate bonds formed by central metal atom, with the
ligands. e.g., in [PtCI6]2-, Pt has coordination number 6.
In case of monodentate ligands,
Coordination number = number of ligands
In polydentate ligands.
Coordination number = number of ligands * denticity
6. Coordination Sphere
The central ion and the ligands attached to it are enclosed in square bracket which is
known as coordination sphere. The ionisable group written outside the bracket is known
as counter ions.
7. Coordination Polyhedron
The spatial arrangement of the ligands which are directly attached to the central atom or
ion, is called coordination polyhedron around the central atom or ion.
8. Oxidation Number of Central Atom
The charge of the complex if all the ligands are removed along with the electron pairs
that are shared with the central atom, is called oxidation number of central atom.
e.g., [Cu(CN4)3-, oxidation number of copper is +1, and represented as Cu(I).
Types of Complexes
1. Homoleptic complexes
Complexes in which the metal atom or ion is linked to only one kind of donor atoms, are
called homoleptic complexes e.g., [Co(NH3)6]3+
2. Heteroleptic complexes
Complexes in which the metal atom or ion is linked to more than one kind of donor
atoms are called heteroleptic complexes e.g., [Co(NH3)4CI2]+

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 Werner’s Theory:
 Metals possess two types of valencies i.e. primary (ionizable) valency and secondary
(nonionizable) valency.
 Secondary valency of a metal is equal to the number of ligands attached to it i.e.
coordination number.
 Primary valencies are satisfied by negative ions, while secondary valencies may be
satisfied by neutral, negative or positive ions.
 Secondary valencies have a fixed orientation around the metal in space.
[Co(NH3)6]Cl3
Primary Valencies = 3 Cl-
Secondary Valencies = 6 NH3
Coordination Sphere = [Co(NH3)6]3-
NOMENCLATURE OF COCORDINATION COMPOUNDS (IUPAC RULES)
 To name a coordination compound, no matter whether the complex ion is the cation
or the anion, always name the cation before the anion. (This is just like naming an
ionic compound.)
Example: [Co(NH3)6]Cl3 hexaammine cobalt (III) chloride.
K2[PtCl6] potassium hexachloroplatinate (IV).
 Name is started with a small letter and the complex part is written as one word.
 For non-ionic or molecular complexes one word name is given
[CO(NO2)3 (NH3)3] triamminetrinitrocobalt (III)

Naming of ligands
 Negative ligands are named by adding suffix - o. (change –ide to –ido, ite to ito, ate
to ato) Example: CN- (cyano) Cl- (chloro) SO42- (sulphato)
 Positive ligands are named by adding prefix – ium.
Example: NO2+ (nitronium), NO+(nitrosonium)

 Neutral ligands are named as such without adding any suffix or prefix.
Example: NH3 (ammine) H2O (aqua) CO (Carbonyl) NO (Nitrosyl).
In unidentate ligands with more than one co-ordinating atoms (ambidentate ligands)
the point of attachment is designated. Example: - SCN thiocyanato or thiocyanato –
S, - NCS isothiocyanato or thiocyanato-S

Ligands Name
Negative
CH3COO- Acetato
CN- Cyanido
Br- Bromido

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 Cl- Chlorido
F- Fluorido
OH- Hydrido
N3- Nitrido
C2O42- Oxalato
SO32- Sulfito
O2- Superoxo
O22- Peroxo
O2- Oxo
NH2- Imido
SO42- Sulphato
S2O32- Thiosulfato
HS- Mercapto
Positive
NO+ Nitrosonium
NH2NH3+ Hydrazinium
Neutral
H2O Aqua
NH3 Ammine
CO Carbonyl
CH3NH2 Methylamine
NO Nitrosyl
C5H5N Pyridine
Prefixes
 If several ligands of the same type are present the prefix di, tri, tetra, penta and hexa
are used.
 For polysyllabic ligands i.e. ligands which have numbers in their name like
hexamethylenediamine the prefix bis, tris and tetrakis are used.
Preference order
 All ligands are named in alphabetical order. The prefix di, tri are not considered.

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 Example: [PtCl(NO2)(NH3)4] SO4
Tetra ammine chloronitro platinum (IV) sulphate.
Naming the complex
Ligands are named first followed by the metal atom. The ending of the name of the
metal depends on the nature of the complex ion.
a) If the complex ion is a cation or non-ionic, the name of the central metal ion is written
as such followed by its oxidation state, indicated by roman numerals (II, III, IV).
Example:
i) [Cu(NH3)4]SO4 Tetramminecopper (II) sulphate
ii) [Pt Cl4 (NH3)2] Diammine tetrachloroplatinum (IV).
b) If the complex ion is an anion the name of the central metal atom is made to end in -
ate.
Example: Na3 [AlF6] sodium hexafluoro aluminate (III)
c) When both cation and anion are complex ions, the metal in negative complex is
named by adding suffix-ate.

Name the following complexes:

1.[NiCl4]2− 2. [CuNH3Cl5]3− 3. [Cd(en)2(CN)2]
4.[Co(NH3)5Cl]SO4 5. [Cr(NH3)3(H2O)3]Cl3 6. [Pt(NH3)5Cl]Br3
7. [Pt(H2NCH2CH2NH2)2Cl2]Cl2 8. Fe(CO)5
Answers:
1. tetrachloronickelate(II) ion 2. amminepentachlorocuprate(II) ion
3. dicyanobis(ethylenediamine)cadmium(II) 4. pentaamminechlorocobalt(III) sulfate
5. triamminetriaquachromium(III) chloride 6. pentaamminechloroplatinum(IV)
bromide
7. dichlorobis(ethylenediamine)platinum(IV) chloride
8. pentacarbonyliron(0)

Isomerism in coordination compounds

Structural Isomerism
 Ionization Isomerism: Exchange of ligands between coordinate sphere and ionization
sphere
[Pt(NH3)4Cl2]Br2 & [Pt(NH3)4Br2]Cl2
 Hydrate Isomerism: Exchange of water molecules between coordinate sphere and
ionization sphere
[Cr(NH3)3(H2O)3]Br3 & [Cr(NH3)3(H2O)2 Br]Br2 H2O
 Linkage Isomerism: Ambient legend binds from the different binding sites to the
metal atom.
K2[Cu(CNS)4] & K2[Cu(SCN)4]
 Coordination Isomerism: Exchange of the metal atom between coordinate sphere
and ionization sphere when both are complex ions.
[Cr(NH3)6][CoF6] & [Co(NH3)6][CrF6].

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 Ligand Isomerism: Different isomers of the same ligands attached to the metal.
[Co(pn)2Br]Cl2&[Co(tn)2Br]Cl2 Where,
pn = 1,2- Diaminopropane tn = 1,3-Diaminopropane.

Stereoisomerism:
a.Geometrical Isomerism: When two similar ligands are on adjacent position the isomer
is called cis isomer while hen they are on opposite positions, the isomer is called trans
isomer.

b.Optical Isomerism: In order to show optical isomerism, the complex should form a non
superimposible mirror image which rotates the place of polarized light in opposite
direction.
Valence Bond Theory:
Hybridization:
Find out the hybridization of central metal ion using following steps:
 Write down the electronic configuration of metal atom.
 Find out oxidation state of metal atom.
 Write down the electronic configuration of metal ion.
 Write down the configuration of complex to find out hybridization.
 Strong field ligands cause the pairing of electrons.
Strong Field Ligands: CO, CN-, NO2-, en, py, NH3.
Weak Filed Ligands: H2O, OH-, F-, Cl-, Br-,I -
When the d orbital taking part in hybridization is inside the s and p orbital, it is called an
inner orbital complex. Example: d2sp3 hybridization of [Co(NH3)6]3+ involves 3d, 4s and
4p orbital, hence it is an inner orbital complex.
When the d orbital taking part in hybridization outside the s and p orbital, it is called an
outer orbital complex.
Example: sp3d2 hybridization of [CoF6]3- involves 4d, 4s and 4p orbital, hence it is an
inner orbital complex.

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Geometry:
Coordination Number Hybridization Geometry

4 sp3 Tetrahedral

dsp2 Square Planar

6 d2sp3 & sp3d2 Oct

Magnetic Properties:
 Diamagnetic: All the electrons paired.
 Paramagnetic: Contains unpaired electrons.
Colour:
Compound must contain free electrons in order to show colour.
Crystal Field Theory:
Strong field ligand causes greater repulsion and thus results in the formation of low spin
complexes by pairing of electrons.
 Weak field ligands result in the formation of high spin complexes
 Order of strength of ligands:

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 Octahedral Complexes: eg orbital are of higher energy than t2g orbital.

 Tetrahedral Complexes: eg orbitals are of lower energy than t2g orbitals.

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For the same metal, the same ligands and metal-ligand distances, the difference in
energy between eg and t2g level is Δt = (4/9) Δo
Metal carbonyls:
a) Metal carbonyls are homoleptic complexes in which
carbon monoxide (CO) acts as
the ligand.
b) Example: Ni(CO)4
c) The metal-carbon bond in metal carbonyls possess both s
and p character.
d) The M–C σ bond is formed by the donation of lone pair of
electrons from the carbonyl
carbon into a vacant orbital of the metal.
e) The M–C pi bond is formed by the donation of a pair of
electrons from a filled d
orbital of metal into the vacant antibondingp* orbital of carbon monoxide.
f) The metal to ligand bonding creates a synergic effect which strengthens the bond
between CO and the metal.
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