Professional Documents
Culture Documents
Coordination Compounds Anil Hsslive
Coordination Compounds Anil Hsslive
Square planar complexes of the type MABXL (where A, B, X, L are unidentate ligands) show three geometrical
isomers-two cis and one trans.
Octahedral complexes with formula [MX2L4] can also show this type of isomerism. Here the two ligands X may be
oriented cis or trans to each other.
e.g.: [Co(NH3)4Cl2]+
This type of isomerism also arises when bidentate ligands (L – L) are present in complexes with formula [MX2(L –
L)2] e.g.: [Co (en)2Cl2]+
Tetrahedral complexes do not show geometrical isomerism because in a tetrahedron all the positions are equivalent.
So the relative positions of the ligands attached to the central metal atom are the same with respect to each other.
ii) 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.
There are two forms of optical isomers - 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 bidentate ligands.
In a co-ordination entity of the type [PtCl2(en)2]+, only the cis-isomer shows optical activity. The trans- isomer has
a plane of symmetry and is optically inactive.
1) In co-ordination 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 co-ordination number of the
metal atom.
2) The vacant orbitals of the metal undergo hybridisation to form a set of new orbitals called hybrid orbitals. The type of
hybridisation gives the shape of the compound.
3) Tetrahedral, square planar and octahedral complexes are formed as a result of sp3, dsp2 and d2sp3 (sp3d2)
hybridisation respectively.
4) Each ligand should contain at least one pair of electron.
5) The vacant hybrid orbitals of the metal overlap with the filled orbitals of the ligands to form ligand – metal co-
ordinate bond.
6) If a complex contains unpaired electron, 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 from the knowledge of its magnetic behaviour on the
basis of the valence bond theory.
E.g.: 1) [Fe(CN)6]3-
Here the central atom Fe is in +3 oxidation state.
26Fe – [Ar]3d64s2
Fe - [Ar]3d5 4s04p0
3+
4s 4p
3+
Fe - ↑ ↑ ↑ ↑ ↑
In this complex, the co-ordination number of Fe is 6 and hence the no. of vacant orbitals required = 6. In presence
of the ligand CN-, the electrons in 3d level get paired.
↑↓ ↑↓ ↑
↑↓ ↑↓ ↑ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓
3-
2) [FeF6]
4s 4p
3+
Fe - ↑ ↑ ↑ ↑ ↑
In this complex the co-ordination number of Fe is 6 and hence the no. of vacant orbitals required = 6. In presence
of the ligand F-, the electrons in 3d level do not get paired.
3d 4s 4p 4d
↑ ↑ ↑ ↑ ↑
Now the one 4s orbital, three 4p orbitals and two 4d orbitals undergo sp3d2 hybridization to form 6 new orbitals. These
hybrid orbitals overlap with the filled orbitals of the ligand to form ligand– metal co-ordinate bond.
↑ ↑ ↑ ↑ ↑ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓
3 2
Since the hybridization is sp d , the shape of the molecule is octahedral and due to the presence of 5 unpaired
electrons, it is highly paramagnetic. In the formation of this complex, since the outer orbitals (4d ) are used for
hybridisation (sp3d2), it is called outer orbital or high spin or spin free complex.
3) [Ni(CN)4]2-
Here the central atom Ni is in +2 oxidation state.
28Ni – [Ar]3d84s2
Ni 2+ - [Ar]3d8 4s04p0
4s 4p
Ni2+ - ↑↓ ↑↓ ↑↓ ↑ ↑
In this complex the co-ordination number of Ni is 4 and hence the no. of vacant orbitals required = 4. Even
though it contains 4 orbitals, in presence of the ligand CN-, the electrons in 3d level get paired.
↑↓ ↑↓ ↑↓ ↑↓
↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓
In this complex the co-ordination number of Ni is 4 and hence the no. of vacant orbitals required = 4. In presence
of the ligand Cl-, the electrons in 3d level do not get paired.
3d 4s 4
↑↓ ↑↓ ↑↓ ↑ ↑
Now the one 4s orbitals and three 4p orbitals undergo sp3 hybridization to form 4 new orbitals. These four hybrid
orbitals are occupied by the four electron pairs from each Cl- ligands. Thus, the complex has tetrahedral geometry and is
paramagnetic because of the presence of unpaired electron.
↑↓ ↑↓ ↑↓ ↑ ↑ ↑↓ ↑↓ ↑↓ ↑↓
Strong field ligands produce large splitting whereas weak field ligands produce small splitting of d orbitals.
Filling of electrons
For d1, d2 and d3 coordination entities, the d electrons occupy the t2g orbitals singly in accordance with the Hund’s
rule. For d4 ions, two possible patterns of electron distribution arise:
(i) the fourth electron could either enter the t2g level and pair with an existing electron, or
(ii) it could enter into the eg level.
Here the electron distribution depends on the relative magnitude of the crystal field splitting (Δo) and the pairing
energy (P). If Δo < P, the fourth electron enters one of the eg orbitals giving the configuration t2g3eg1. Ligands for which Δo
< P are known as weak field ligands and form high spin complexes.
If Δo > P, the fourth electron occupy a t2g orbital with configuration t2g4eg0. Ligands for which Δo < P are known as
strong field ligands and form low spin complexes.
a) Crystal field splitting in Tetrahedral coordination entities (tetrahedral field)
A tetrahedron can be considered as a cube in which only alternate corners are occupied by ligands and the metal
ion is at the centre of the cube. The dx2-y2 and dz2 orbitals (called e orbitals) point towards the centre of each faces of the
cube and the dxy, dyz and dxz orbitals (called t2 orbitals) point towards the edge centre of the cube. Since the ligands are
approaching through the corners, there is no direct interaction between the ligands and the d-orbitals. However, the ‘t2’
orbitals lie closer to the ligands than the ‘e’ orbitals. As a result the energy of the ‘t2’ orbitals increases and that of ‘e’
orbitals decreases. So the d orbitals split into two – triply degenerate ‘t2’ orbitals with higher energy and doubly
degenerate ‘e’ orbitals with lower energy.
The metal-carbon bond in metal carbonyls possess both s and p 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 anti-bonding π* orbital of carbon
monoxide. Thus the metal to ligand bonding creates a synergic effect which strengthens the bond between CO and the
metal.
&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&