CO-ORDINATION COMPOUNDS

TRANSITION METALS
PROPERTIES
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Colour
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Many compounds of transition elements are coloured in contrasts to those
of s and p block elements.
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In compound state due to the surrounding groups (ligands), the d-orbitals of
transition elements are not degenerate but split into two groups of different
energy.
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Thus it is possible to promote electrons from one group to another group.
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This corresponds to fairly small amount of energy difference and so light is
absorbed in visible region. Some compounds of transition metals are white,
for example ZnSO4 and TiO2. In these compounds it is not possible to
promote the electrons within the d-level.
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Variable Oxidation State
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Magnetic property
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On the basis of behaviour in a magnetic field, substance are
classified as paramagnetic, diamagnetic and ferromagnetic.
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Those substance which are attracted by the applied magnetic field
are called paramagnetic where as those which are repelled by the
magnetic field are called diamagnetic.
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Substances which are very strongly attracted by the applied field are
called ferromagnetic.
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Paramagnetism is a property due to the presence of unpaired
electrons. Thus most of the transition metals are paramagnetic.
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As the number of unpaired electrons increases, the paramagnetic
character also increases.
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Catalytic property
Many transition metals and their compounds have catalytic
properties. For e.g. V2O5, Fe, FeCl3, Ni, Pd etc.
This is due to following reasons
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Variable oxidation state: Due to variable oxidation state they form
unstable intermediate compounds and provide a new path with lower
activation energy for the reaction (Intermediate compound formation
theory)
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Large Surface area: Finely divided transition metals or their
compounds provide a large surface area for adsorption and the
adsorbed reactants react faster due to the closer contact.
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Complexation tendency:
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The transition elements have an unparalleled
tendency to form coordination compounds with the
Lewis bases.
CO3+ + 6NH3 → [CO(NH3)6]3+
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NOMENCLATURE OF
CO-ORDINATION
COMPOUNDS
 Examples Based on Postulates of Werner’s
Theory
Cobalt has a primary valency (oxidation state) of three and
exhibits secondary valency (coordination number) of 6. We
represent the secondary valencies by thick lines and the primary
valency by broken lines.
1)CoCl3.6NH3 Complex: In this compound, the coordination number of cobalt
is 6 and all the 6 secondary valencies are satisfied by NH3 molecules (the
black solid lines). The 3 primary valencies are satisfied by chloride ions (the
dotted line in fig). These are non-directional in character. These chloride ions
are instantaneously precipitated on the addition of silver nitrate. The total
number of ions in this case is 4, three chloride ions and one complex ion. The
central ion and the neutral molecules or ions satisfying secondary valencies are
written in a square bracket while writing the formula of the compound. Hence
the complex may be written as [Co(NH3)6]Cl3 and as shown as in fig.
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2) CoCl3.5NH3 complex: In this compound the coordination
number of cobalt is also 6 but the number of NH3 molecule is
decreased to 5 from 6 and one remaining position is now
occupied by chloride ion. This chloride ion exhibits the dual
behaviour as it has primary as well as secondary valency.
Secondary valency is shown by full line and the primary
valency is shown by dotted line in the figure.
3)​​CoCl3.4NH3 complex: In this compound, two chloride ions
exhibit dual behaviour of satisfying both Primary and
Secondary Valencies. This compound will give precipitate
with silver nitrate corresponding to only one Cl- ion and the
total number of ions in this case is 2. Hence it can be
formulated as [CoCl2(NH3)4]Cl
4)CoCl3.3NH3 complex: In this compound, three chloride
ions satisfy primary as well as secondary valency. No Cl- will
be precipitated on the addition of silver nitrate at room
temperature. Therefore, the complex compound behave as
neutral non conducting molecule. It may be formulated as
[CoCl3(NH3)3]
Stability of complexes
Valence Bond Theory
According to this theory
• the metal atom or ion under the influence of
ligands can use its (n-1)d, ns, np, nd orbitals
for hybridisation. This would lead to a yield a
set of equivalent orbitals of definite geometry.
• These include octahedral, tetrahedral, square
planar and other such geometrical
arrangements. The hybridised orbitals can
overlap with the ligand orbitals. These orbitals
are ready to donate valence electrons /
electron pairs for bonding.