CHAPTER-5

Addition or Molecular Compounds

Two salts mixed together in simple proportions
form Addition or Molecular compounds.

FeSO4 + (NH4)2SO4 + 6H2O → FeSO4.(NH4)2SO4

.6H2O
Fe(CN)2 + 4KCN → K4 [Fe(CN)6]
Double salts Complex salt/ Cordination
Compounds

dissociate into simple ions Complex ions such as

completely when dissolved [Fe(CN)6]4- does not
in water. dissociate into Fe2+ and CN-
ions.
KCl.MgCl2.6H2O,
K4 [Fe(CN)6]
Mohr's salt
(FeSO4.(NH4)2SO4.6H2O) [Co(H2O)6 ]Cl2
 Co-ordination Compound
Ligand
Central metal Counter
ion ion

[Cu(NH3)4]Cl2
Coordination sphere
Coordination entity
Constitutes a central metal atom or ion bonded
to fixed number of ions or molecules.

Central metal ion

Cation to which one or more neutral
molecules or anions is attached.
Ligand
An atom or group of atoms which binds to the
central atom through the lone pair of electrons
present in its donor atoms.

The atom of the ligand which is directly bonded to

the central atom is called as donor atom.
may be simple ions such as Cl–

small molecules such as H2O or NH3 ,

larger molecules such as H2NCH2CH2NH2

or N(CH2CH2NH2 )3
 Types of Ligands
Monodentate or Unidentate ligands
ligand bound to a metal ion through a single donor
atom.
Eg : 𝐂𝐂𝐂𝐂− , H2O, NH3, 𝐁𝐁𝐁𝐁 − ,𝐎𝐎𝐎𝐎 −
Didentate or Bidentate ligands
ligand binding through 2 donor atoms.
Eg : H2NCH2CH2NH2 (Ethane-1,2- diamine) ,
C2O42- (Oxalate)
Polydentate ligands
ligand can bind through more than 2 donor atoms.
Eg : N(CH2CH2NH2)3 (Triethylamine ammonia) ,
𝐄𝐄𝐄𝐄𝐄𝐄𝐄𝐄𝟒𝟒− (Ethylenediaminetetraacetate ion)

EDTA4- (Ethylenediaminetetraacetate ion)

No of Donor Atoms = 6
( 4 Oxygen atoms & 2 Nitrogen atoms)
Called as Hexadentate Ligand
Ambidentate ligand
are monodentate ligands.
can bind through two different atoms
present in it.
Eg : NO2- , SCN-
Chelating ligand
When a bidentate or polydentate ligand binds to a
central atom and forms a ring like structure called
chelate .
ligand is known as chelating ligand.
Chelating ligands form more stable coordination
compounds.
Coordination sphere
The central atom along with ligands surrounding it
are written in square bracket [] , is called as
coordination sphere.

Coordination number
The total number of ligand donor atoms
surrounding the central atom in a coordination
sphere.
Charge on complex
The sum of oxidation number of all the atoms
/molecules or ions constituting the coordination
sphere.

Coordination polyhedron
The spatial arrangement of ligand atoms around
the central atom.
 Homoleptic Heteroleptic
complexes complexes
Complexes in which a Complexes in which a
metal is bound to only metal is bound to
one kind of ligand. more than one kind of
[Co(NH3)6]3+ ligands.
[Co(NH3)4Cl2]+
IUPAC NOMENCLATURE OF COORDINATION
COMPOUNDS
(i) The cation is named first
in both positively and
negatively charged co-
ordination entities.
(ii) The ligands are named in
alphabetical order before the
name of the central
atom/ion.
IUPAC NOMENCLATURE OF COORDINATION
COMPOUNDS
(iii) Names of the anionic
ligands end in- o, those of
neutral and cationic ligands
are the same except “aqua” for
H₂O, “ammine” for NH3 ,
“carbonyl” for CO and
“nitrosyl” for NO.
 IUPAC NOMENCLATURE OF COORDINATION
COMPOUNDS
(iv) Prefixes mono, di, tri, etc.
are used to indicate the
number of individual ligands
in the co- ordination entity.
(v) Oxidation state of the
metal is indicated by Roman
numeral in simple bracket.
IUPAC NOMENCLATURE OF COORDINATION
COMPOUNDS
(vi) When the names of the
ligands include a numerical
prefix, then the terms bis (for
2 such ligands), tris (for 3),
tetrakis (for 4) are used. Here
the name of the ligand is
placed in simple bracket.
IUPAC NOMENCLATURE OF COORDINATION
COMPOUNDS
(vii) If the complex ion is a cation,
the central atom is named same
as the element. If the complex
ion is an anion, the name of the
metal ends with the suffix- ate.
For example ferrate for Iron,
cobaltate for Cobalt, zincate for
Zinc
IUPAC NOMENCLATURE OF COORDINATION
COMPOUNDS
(viii) The neutral complex
molecule is named similar
to that of the cationic
complex.
 Cl- Chlorido / Chloro NCS- Isothiocyanato

Br- Bromido / Bromo SO42- Sulphato

I- Iodido / Iodo NO2- Nitrito - N

F- Fluorido / fluoro ONO- Nitrito - O

NH3 Ammine
CN- Cyanido / Cyano
H2O Aqua
CO32- Carbonato
NH2CH2CH2NH2 Ethane – 1 , 2 -
C2O42- Oxalato diamine
SCN- Thiocyanato CO Carbonyl
 Ionisation isomerism
This arises when the coordination compounds with
same molecular formula gives different ions in
solution
[Co (NH3)5Br]SO4 and [Co (NH3)5SO4]Br
Linkage isomerism
It arises in complexes containing monodentate ligands
with more than one donor atom.
[Co (NH3)5NO2]Cl2 and [Co (NH3)5ONO]Cl2
 Coordination isomerism
This type of isomerism is possible when both positive and
negative ions of salt are complex ions. It involves exchange
of ligands between complex cation and complex anion
[Cr(NH3)6] [Co(CN)6] and [Co(NH3)6] [Cr(CN)6]

Hydrate isomerism
It arises in complexes due to different number of water
molecules present in the coordination spheres.
[Cr(H2O)6]Cl3 and [Cr(H2O)5Cl]Cl2.H2O
STEREOISOMERISM
 Geometrical isomerism or cis-trans isomerism
Arises when ligands occupy different positions around the
central atom. The ligands occupy positions adjacent to one
another is referred as cis form and opposite to one another is
referred as trans form.
a)Square planar complexes

Cis Trans
b)Octahedral complexes
c)Fac-mer isomerism
 Optical isomerism
Optical isomers are mirror
images that cannot be
superimposed on one another.
These are also called
Enantiomers.
The molecules or ions that
cannot be superimposed are
called chiral.
The two forms are called
dextro (d) and laevo (l)
depending upon the direction
they rotate the plane of
polarised light. (d rotates to
the right, l to the left).
Optical activity is the ability
of a compound to rotate the
plane of plane polarised light.
 THEORIES
OF COORDINATION
COMPOUNDS
WERNER'S COORDINATION THEORY
1. In coordination compounds
metals show two types of
linkages (valences)- Primary and
Secondary.
2. The primary valences are
normally ionisable and are
satisfied by negative ions.
WERNER'S COORDINATION THEORY
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.
 THE VALENCE BOND THEORY (VBT)
1) In coordination compounds,
the central metal atom/ion
provides some vacant orbitals in
order to accommodate the
electrons donated by the
ligands. The number of vacant
orbitals formed is equal to the
coordination number of the
metal atom.
THE VALENCE BOND THEORY (VBT)
2) The vacant orbitals of
the metal undergo
hybridization to form a set
of new orbitals called
Hybrid orbitals. The type of
hybridization gives the
shape of the compound.
3) Each ligand should contain at
least one pair of electron
4) The vacant hybrid orbitals of
the metal overlap with the filled
orbitals of the ligands to form
ligand metal coordinate bond
5) If a complex contains unpaired
election, it is paramagnetic and if
it contains only paired electron,
it is diamagnetic.
Applications of VBT
It is usually possible to predict the Geometry of a
complex and its Magnetic behavior on the basis of the
valence bond theory.
1) [Fe CN6 ]3−
2) [FeF6 ]3−
3) [Ni(CN)4 ]2−
4) [Ni(Cl)4 ]2−
 SPECTROCHEMICAL SERIES
It is a series in which the ligands are arranged in
the increasing order of their field strength.It is an
experimentally determined series based on the
absorption of light by complexes with different
ligands.
CRYSTAL FIELD
THEORY
Weak and Strong ligand conditions
Bonding in metal carbonyls
 Bonding in metal carbonyls
The metal-carbon bond in metal carbonyls possess both
σ and π character.
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.
APPLICATION OF CO- ORDINATION COMPLEXES
1. In Qualitative & Quantitative Analysis: Example: Ni2+ is
detected and estimated by the formation of a complex with Dimethyl
Glyoxime (DMG). The brown ring test for the detection of nitrate ion
is due to the formation of brown complex [Fe(H𝟐𝟐 𝐎𝐎) 5NO]2+ . The Ca2+
and 𝐌𝐌𝐌𝐌 𝟐𝟐+ ions are estimated by the formation of stable complexes
with EDTA.
2. In water treatment: The hardness of water is estimated by
simple titration with Na𝟐𝟐 EDTA (sodium salt of EDTA). The Ca2+ and
𝐌𝐌𝐌𝐌 𝟐𝟐+ ions form stable complexes with EDTA. The hardness of water
can be removed by the formation of a complex with calgon (Sodium
polymetaphosphate).
3. In Metallurgy: Metals like silver and gold are extracted by the
formation of complexes with 𝐂𝐂𝐂𝐂 − ligands. Gold forms the complex
[Au(𝐂𝐂𝐂𝐂)𝟐𝟐 ]- and silver forms [Ag(𝐂𝐂𝐂𝐂)𝟐𝟐 ]- which are separated with
Zn. Similarly, coordination compounds also find application in the
refining of some metals. For example, impure nickel is converted to
[Ni(𝐂𝐂𝐂𝐂)𝟒𝟒 ], which is decomposed to yield pure nickel.
4. Biological Applications: Coordination compounds are of great
importance in biological systems.
Chlorophyll- Coordination compound of magnesium
Haemoglobin- Coordination compound of iron
Vitamin B12 (cyanocobalamine)- Coordination compound of cobalt
5. In Catalysis: Co- ordination compounds are used as
catalysts for many industrial processes. For e.g.:
Tris(triphenylphosphine) rhodium chloride
[(PP𝑯𝑯𝟑𝟑 )𝟑𝟑 RhCl] (Wilkinson catalyst) is used for the
hydrogenation of alkenes.
6. In electroplating: Articles can be electroplated with
silver and gold by using the solutions of the
complexes, [Ag(𝐂𝐂𝐂𝐂)𝟐𝟐 ]- and [Au(𝐂𝐂𝐂𝐂)𝟐𝟐 ]- respectively as
electrolytes.
7. In Photography: 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 (𝑺𝑺𝟐𝟐 𝑶𝑶𝟐𝟐 )]𝟐𝟐 - .
8. In medicine: Cis- platin is used for the treatment of
cancer. Excess of copper and iron in animal or plant
body are removed by the chelating ligands D-
penicillamine and desferrioxine B through the
formation of co-ordination compounds. EDTA is used
in the treatment of lead poisoning.
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