Coordination Compounds

Some Important Terms:

❖ Double salts: complexes formed by the combination of two or more Alfred Werner, propounded his
stable compounds. Can be dissociate into simple ions completely when theory of coordination compounds.
dissolved in water. Eg: Carnallite, (KCl.MgCl2 .6H2O) Mohr’s salt, (FeSO4 The main postulates are:
.(NH4 )2SO4 .6H2O) potash alum etc. 1. In coordination compounds metals
❖ Complex ions: do not dissociate into ions. show two types of linkages- primary
❖ Coordination entity: constitutes a central metal atom or ion bonded to and secondary.
a fixed number of ions or molecules. Eg: [CoCl3 (NH3 )3 ]
❖ Central atom/ion: the atom/ion to which a fixed number of ions/groups 2. The primary valences are normally
are bound in a definite geometrical arrangement around it. ionisable and are satisfied by negative
ions.
❖ Ligands: The ions or molecules bound to the central atom/ion. If it is
bound to a metal ion through a single donor atom, the ligand is said to be 3. The secondary valences are non
unidentate. If through two donor atoms the ligand is said to be ionisable. These are satisfied by
didentate. If several donor atoms are present in a single ligand the ligand neutral molecules or negative ions.
is said to be polydentate. When a di- or polydentate ligand uses its two or The secondary valence is equal to the
more donor atoms simultaneously to bind a single metal ion, it is said to coordination number and is fixed for a
be a chelate ligand. The number of such ligating groups is called the metal.
denticity of the ligand. Chelate complexes are more stable than
complexes containing unidentate ligands. Ligand which has two different 4. The ions/groups bound by the
donor atoms and either of the two ligetes in the complex is called secondary linkages to the metal have
ambidentate ligand. characteristic spatial arrangements
corresponding to different
❖ Coordination number: The number of ligand donor atoms to which the
coordination numbers.
metal is directly bonded.
❖ Coordination sphere: The central atom/ion and the ligands attached to
it are enclosed in square bracket. The ionisable groups are written outside the bracket and are called counter
ions.
❖ Coordination polyhedron: The spatial arrangement of the ligand atoms which are directly attached to the
central atom/ion.
❖ Oxidation number of central atom: The charge it would carry if all the ligands are removed along with the
electron pairs that are shared with the central atom.
❖ Homoleptic Complexes: Complexes in which a metal is bound to only one kind of donor groups.
❖ Heteroleptic Complexes: Complexes in which a metal is bound to more than one kind of donor groups.

Mononuclear compound
Formula; (i) Central atom is listed first.
(ii) The ligands are then listed in alphabetical order. (does not depend on its charge)
(iii) Polydentate ligands are also listed alphabetically.
(iv) The formula for the entire coordination entity, is enclosed in square brackets.
(v) There should be no space between the ligands and the metal within a coordination sphere.
(vi) When the formula of a charged coordination entity is to be written without that of the counter ion, the charge is
indicated outside the square brackets as a right superscript with the number before the sign.
(vii) The charge of the cation(s) is balanced by the charge of the anion(s).

Nomenclature; (i)The cation is named first in both positively and negatively charged coordination entities.
(ii) The ligands are named in an alphabetical order before the name of the central atom/ion.

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(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. While writing the formula of coordination entity, these are
enclosed in brackets ( ).
(iv) Prefixes mono, di, tri, etc., are used to indicate the number of the individual ligands in the coordination entity.
When the names of the ligands include a numerical prefix, then the terms, bis, tris, tetrakis are used.
(v) Oxidation state of the metal in cation, anion or neutral coordination entity is indicated by Roman numeral.
(vi) If the complex ion is a cation, the metal is named same as the element. The neutral complex molecule is named
similar to that of the complex cation.

ISOMERISM
Isomers are two or more compounds that have the same chemical formula but a different arrangement of atoms.
Because of the different arrangement of atoms, they differ in one or more physical or chemical properties.
❖ STEREOISOMERISM :Stereoisomers have the same chemical formula and chemical bonds but they have
different spatial arrangement.
➢ Geometrical isomerism : This type of isomerism arises in heteroleptic complexes due to different
possible geometric arrangements of the ligands. Important examples of this behaviour are found with
coordination numbers 4 and 6. Square planar complexes and octahedral complexes shows this isomerism.
Eg: Pt[(NH3)2Cl2] [Co(NH3)4Cl2]+ [CoCl2(en)2] form cis and trans isomer. [Co(NH3)3(NO2)3]
Geometrical isomerism not possible in tetrahedral complexes having two different types of unidentate ligands
coordinated with the central metal ion , because the relative positions of the unidentate ligands attached to the
central metal atom are the same with respect to each other.
➢ Optical isomerism : Optical isomers are mirror images that cannot be superimposed on one
another. These are called as 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 in a polarimeter (d rotates to the right, l to the left). Optical isomerism is common in
octahedral complexes involving didentate ligands. Eg: [PtCl2 (en)2 ] 2+, only the cis-isomer shows optical
activity.
❖ STRUCTURAL ISOMERISM : Structural isomers have different bonds.
➢ Linkage isomerism : Arises in a coordination compound containing ambidentate ligand. Eg:
complexes containing the thiocyanate ligand, NCS– .
➢ Coordination isomerism : This type of isomerism arises from the interchange of ligands between
cationic and anionic entities of different metal ions present in a complex.
Limitations of Werners theory:
Eg: [Co(NH3 )6 ][Cr(CN)6 ]
➢ Ionisation isomerism : This form of isomerism arises when the counter • Why only certain elements
ion in a complex salt is itself a potential ligand and can displace a ligand possess the remarkable
which can then become the counter ion. Eg: [Co(NH3 )5 (SO4 )]Br and property of forming
[Co(NH3 )5Br]SO4 . coordination compounds?
➢ Solvate isomerism : Also known as ‘hydrate isomerism’ in case where • Why the bonds in
water is involved as a solvent. This is similar to ionisation isomerism. coordination compounds
Solvate isomers differ by whether or not a solvent molecule is directly have directional
bonded to the metal ion or merely present as free solvent molecules in properties?
the crystal lattice. Eg:[Cr(H2O)6]Cl3 (violet) and its solvate isomer • Why coordination
[Cr(H2O)5Cl]Cl2.H2O (grey-green). compounds have
characteristic magnetic and
VALENCE BOND THEORY optical properties?
According to this theory, the metal atom or ion under the influence of ligands can
use its (n-1)d, ns, np or ns, np, nd orbitals for hybridisation to yield a set of equivalent orbitals of definite geometry
such as octahedral, tetrahedral, square planar and so on .These hybridised orbitals are allowed to overlap with
ligand orbitals that can donate electron pairs for bonding.
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 2–
The spin only magnetic moment of [MnBr4 ] is 5.9 BM. Predict the geometry of the
complex ion ?
Since the coordination number of Mn2+ ion in the complex ion is 4, it will be either
tetrahedral (sp3 hybridisation) or square planar (dsp2 hybridisation). But the fact that
the magnetic moment of the complex ion is 5.9 BM, it should be tetrahedral in shape
rather than square planar because of the presence of five unpaired electrons in the d
orbitals.

Limitations of Valence Bond Theory

o It involves a number of assumptions.
o It does not give quantitative interpretation of magnetic data and quantitative interpretation of the
thermodynamic or kinetic stabilities of coordination compounds.
o It does not explain the colour exhibited by coordination compounds.
o It does not make exact predictions regarding the tetrahedral and square planar structures of 4-coordinate
complexes.
o It does not distinguish between weak and strong ligands.

CRYSTAL FIELD THEORY

The crystal field model is successful in explaining the formation, structures, colour and magnetic properties of
coordination compounds to a large extent. Ligands are treated as point charges in case of anions or point dipoles in
case of neutral molecules. The negative field due to ligands in a complex, it becomes asymmetrical and the
degeneracy of the d orbitals is lifted. It results in splitting of the d orbitals.
(a) Crystal field splitting in octahedral coordination entities
The crystal field splitting, ∆o, depends upon the field produced by the ligand and charge on the metal ion. Ligands
can be arranged in a series in the order of increasing field strength as given below:
I – < Br– < SCN – < Cl – < S2– < F – < OH – < C2O4 2– < H2O < NCS – < edta4– < NH3 < en < CN – < CO Such a series is
termed as spectrochemical series. It is an experimentally determined series based on the absorption of light by
complexes with different ligands.
(b) Crystal field splitting in tetrahedral coordination entities

In tetrahedral coordination entity formation, the d orbital splitting (Fig. 9.9) is inverted and is smaller as compared to
the octahedral field splitting.

Limitations : From the assumptions that the ligands are point charges, it follows that anionic ligands should exert
the greatest splitting effect but the anionic ligands actually are found at the low end of the spectrochemical series.
: It does not take into account the covalent character of bonding between the ligand and the central atom.

Applications of Coordination Compounds

▪ Coordination compounds find use in many qualitative and quantitative chemical analysis. Examples of such
reagents include EDTA, DMG (dimethylglyoxime), α–nitroso–β–naphthol, cupron, etc.
▪ Hardness of water is estimated by simple titration with Na2EDTA.
▪ Some important extraction processes of metals, like those of silver and gold, make use of complex
formation.
▪ Purification of metals can be achieved through formation and subsequent decomposition of their
coordination compounds.
▪ Coordination compounds are used as catalysts for many industrial processes.