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INTRODUCTION: The concept of co-ordination compounds arises from the complex formation tendency of transition elements.
Molecular or addition compounds:
AgCN + KCN(simple stable compounds) → KCN. AgCN (Addition or molecular compounds)
K2SO4 + Al2 (SO4)3 + 24H2O → K2SO4. Al2(SO4)3.24 H2O(Alum)
Double salts or lattice compounds:
The addition compounds which are stable in solid-state only but are broken down into individual constituents when dissolved in water are called double salts or lattice compounds. e.g.Camallite (KCl. MgCl2. 6H2O)
VARIOUS TERMS USED IN COORDINATION COMPOUNDS
1. Central ion: (Centre of coordination)
2. Ligand: Ligands are normally polar molecules like NH3 ; H2O or anions such as Cl–, OH–, CN– etc.
3. Types of Ligands on the basis of number of donor atoms present in them:
(A) Mono or unidentate ligands:
e.g : F–, Cl–, Br–, H2O, NH3, CN–, NO2–, ON–, CO
(B) Bidentate ligands:
Ligands which have two donor atoms and have the ability to link with central metal ion at two positions are called bidentate ligands. Some examples are:
Ethylenediamine (en)
Oxalate (ox)
1, 10-Phenanthroline (o-phen)
Glycinato (Gly)
2,2′ -Dipyridyl (Dipy)
Carbonato
(C) Tridentate ligands:
The ligands having three donor atoms are called tridentate ligands. Examples are :
Diethylene triamine (Dien)
2,2’,2”-Terpyridine (terpy)
(D) Petradentate ligands:
These ligands possess four donor atoms. Examples are:
(Nitriloacetato)
Triethylene tetramine (Trien)
(E) Pentadentate ligands:
They have five donor atoms. For example, ethylenediamine triacetate ion.
Ethylenediamine triacetato ion
(F) Hexadentate ligands:
They have six donor atoms. The most important example is ethylenediamine tetraacetateion.
Ethylenediamine tetraacetato ion (EDTA)
4. Coordination number:
5. Coordination sphere:
6. Oxidation state:
It is a number which represents the electric charge on the central metal atom of a complex ion. The charge of the complex is the sum of the charges of the constituent parts.
7. Effective atomic number (EAN): EAN = atomic number of the metal- number of electrons lost in. ion formation + number of electrons gained from the donor atoms of the ligands
Nomenclature :
Name of the ligand:
(a) Anionic ligands ending with ‘ide’ are named by replacing ‘ide’ by suffix ‘O’.
Symbol | Name as ligand |
N– | Nitrido |
Cl– | Chloro/chlorido |
O22- | Peroxo |
Br– | Bromo bromido |
O2H– | Perhydroxo |
CN– | Cyano |
S2- | Sulphido |
O2- | Oxo |
NH2- | Ami do |
OH– | Hydroxo |
(b) Ligands whose names end in ‘ite’ or ‘ate’ become ‘ito’ or ‘ato’ i.e., by replacing the ending *e’ with ‘o’ as follow s
Symbol | Name as ligand |
CO32- | Carbonato |
C2O42- | Oxalato |
SO42- | Sulphato |
NO3– | Nitrato |
SO32- | Sulphito |
CH3COO– | Acetato |
NO3– | Nitrito-N |
(c) Neutral ligands are given the same names at the neutral molecules. For example. Ethylene diamine as a ligand is named ethylene diamine in the complex. Flowever some exceptions to this rule are –
HO Aquo
NH3 Ammine CO Carbonyl NO Nitrosyl CS Thiocarbonyl |
(d) Names of positive ligands ends in ‘ium’ e.g.
NH+ (Ammonium)
NO+ (Nitrosylium)
NH2NH3+ (Hydrazinium)
BONDING IN COORDINATION COMPOUNDS
1. Werner’s coordination theory:
(a) Each metal in coordination compound possesses two types of valencies:
2. Valence Bond Theory:
(a) The number of empty orbitals is equal to the coordination number of the metal ion for the particular complex.
(b) The number of unpaired electrons in the complex, points out the magnetic moment and geometry of the complex as well as hybridisation of central metal ion and vice -versa.
Magetic moment μ = \(\sqrt{n(n+2)}\) where n = no of lone pair
(b) Under the influence of a strong ligand (CN, CO etc ) the electrons can be forced to pair up against the Hund’s rule of maximum multiplicity.
• Hybridisation is d2sp3
(c) Hybridisation is sp3d2 in case of weak ligands (X, H2O etc)
3. Drawback of V.B. Theory
4. Crystal Field Theory (CFT)
(a) Splitting in Octahedral complex (Δ0)
(b) Splitting in tetrahedral complex(Δr)
(c) splitting in square planer complex
Factors affecting split
Metal carbonyls
ISOMERISM IN COORDINATION COMPOUNDS
Classification
Ionization isomerism:
This is due to exchange of groups or ion between the coordinating sphere and the ionization sphere
Hydrate isomerism:
This type of isomerism is due to presence of different number of water molecules inside and outside the coordination sphere
violet [Cr (H2O)6]Cl3, green [Cr(H2O)5Cl]Cl2.H2O, dark green [Cr(H2O)4Cl2]Cl.2H2O
Coordination isomerism:
(a) The type of isomerism occurs when both cation and anion are complex.The isomerism is caused by the interchange of ligands between the two complex ions of the same complex. Examples [Co(NH3)6] [Cr(CN)6] and [Cr(NH3)6] [Co(CN)6]
Linkage isomerism :
(a) This type of isomerism arises due to presence of ambidentate ligands like NO2–, CN– CO and SCN–. These ligands have two donor atoms but at a time only one atom is directly linked to the central metal atom of the complex.
Example [CO(NH3)5NO2]Cl2 and [Co(NH3)5 ONO]Cl2
Coordination position isomerism:
This is exhibited by poly nuclear complexes by changing the position of ligands w.r.t. different metal atoms present in the complex
Example
and
Geometrical isomerism:
This isomerism is due to ligands occupying different positions around the central metal atom or ion
Example
Diglycinato platinum (iv) complexes
Stereoisomerism:
> Complex of the type [MA4B2], [MA4BC], [MA2B2] [M(AA)2B2], [M(AA)2BC], [M(AA)B2C2], [MA2B2C2], [M(AB)3] show cis-trans isomerism
> [MA3B3] show fac-mer isomerism
> cis forms of M(AA) B2C2, MA2B2C2, M(AA)2B2 and M(AA)2BC are optically active.
> [M(AA)3], [M(AB)3] are also optically active.
Optical isomerism:
A coordination compound which can rotate the plane of polarised light is said to be optically active. This is due tp the absence of elements of symmetry in the complex
Example : Bis – benzoylacetonato – beryllium (II)
8. STABILITY OF COMPLEX
This can be expressed as follows M + L ⇔ ML where
M = metal and L is ligand. The stability constant K for this reaction is as shown.
High value of K indicate stable complex.
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