Metal ligand bonding in Transition metal complexes

Crystal field theory (CFT) Crystal field theory was developed by scientists Bathe and Van Vleck. CFT explains effect of ligands on metal d-orbitals during formation co-ordinate compounds.

Assumptions The ligands act as point charges, even though they are ions, or neutral molecules. The bonding in between metal and ligands is purely electrostatic (100% ionic). There is The ligand field (crystal field) produced by ligands, splits the originally degenerated Shapes of d-orbitals

1. 2. 3.

neither sharing of electrons nor the overlapping of orbitals. d-orbitals of central metal ion.

dsubshell consists of five orbitals with equivalent energies (degenerated d-orbitals) dxz, dyz, dxy, dx2-y2, dz2. Depending upon their shapes and spacial orientations, they can be divided into two sets : t2g and eg. t2g set t2g set consists of three orbitals dxz, dyz, dxy. These orbitals are identical and have similar spacial orientation. These orbitals consist of 4 lobes and their lobes are oriented in between the axes. i) ii) iii) dxy orbital has 4 lobes oriented in between x & y axis. dyz orbital has 4 lobes oriented in between y & z axis. dxz orbital has 4 lobes oriented in between x & z axis.

eg set eg set consists of two orbitals dx2-y2, dz2. These orbitals are identical and have similar spacial orientation. dx2-y2 orbital has 4 lobes and their lobes are oriented in along x & y axis. dz2 orbital has 2 main lobes oriented in along z axis and a central reduced lobe. Crystal Field splitting in Octahedral Complexes In octahedral complexes, metal is at the centre of octahedron and 6 ligands are at the six corners of that octahedron. Initially before the formation of an octahedral complex, the metal ion is present at the centre of octahedron and x, y & z axes are passing through the corners of that octahedron.

dx2-y2, dz2 (i.e. eg) orbitals of metal are directed along the axes i.e. they are directed

along the axes i.e. they are directed towards corners of octahedron. While dxy, dyz & dxz (i.e. t2g) orbitals of metal ion are directed in between the axes i.e. they are directed towards edge centers of octahedron.

During the formation of octahedral complex, six ligands are approaching towards the central metal ion, along the x, y & z axes. Thus the orbitals pointing along the axes are affected more due to CF produced by ligands i.e. eg orbitals are affected more than t 2g orbitals. So, five degenerated d-orbitals split into two sets eg & t2g having different energies. Diagram: CF splitting due to octahedral field

The difference in energy in between eg & t2g orbitals is given by o or 10Dq. The energy of eg orbitals increases by 6Dq (0.6 o) while energy of t2g orbitals decreases by 4Dq (0.4 o) than the average energy level. Filling of electrons The electrons present in d-orbitals are then filled in splitted t2g & eg orbitals. Electrons are filled according to Hunds rule. In octahedral complex, in which central metal ion has d1 configuration, the electron occupies the available lower energy orbital i.e. t2g orbital. Thus, in d1 case, the configuration is t2g1eg0 . Similarly, for d2 configuration, two electrons occupy t2g orbitals and for d3 configuration, three electrons occupy t2g orbitals. For d4 configuration, the filling of electrons depends upon strength of ligands. If the ligand is weak field, the 4th electron occupies higher energy eg orbital t2g3eg1 (because o<P) and if the ligand is strong field, 4th electron get paired in t2g orbital t2g4eg0 (because o > P).

Similarly, for d5, d6, d7 configurations, the arrangement of electrons are different for SF & WF ligands. SF WF 4 0 d t2g eg t2g3eg1 d5 t2g5eg0 t2g3eg2 d6 t2g6eg0 t2g4eg2 d7 t2g6eg1 t2g5eg2 8 9 10 Again for d ,d ,d configurations, the electronic configurations are similar for SF & WF ligands.
4

d8 d9 d10

t2g6eg2 t2g6eg3 t2g6eg4

t2g6eg2 t2g6eg3 t2g6eg4

Crystal Field Stabilization Energy (CFSE)

In octahedral complexes, the filling of electrons in t2g orbital decreases energy by 4Dq per electron, while filling of electrons in eg orbital increases energy by 6Dq per electron. Total CFSE for octahedral complexes = [(n t2g) (- 4)] + [(n eg) (+6)] where, (n t2g) = no. of electrons in t2g orbitals and (n eg) = no. of electrons in eg orbitals We can calculate CFSE for octahedral complex by using above formula. 1. for d1 configuration, CFSE = [1 (- 4)] + [0 (+6)] = - 4 Dq 2. for d4 configuration, i) For SF ligand complex, the configuration is t2g4eg0 CFSE = [4 (- 4)] + [0 (+6)] = - 16 Dq ii) For WF ligand complex, the configuration is t2g3eg1 CFSE = [3 (- 4)] + [1 (+6)] = - 6 Dq Following table shows the configuration and CFSE for octahedral complexes with WF&SF ligands: WF d
n

SF CFSE Dq o -4 - 0.4 -8 - 0.8 - 12 - 1.2 -6 - 0.6 -0 -0 -4 - 0.4 -8 - 0.8 - 12 - 1.2 -6 - 0.6 -0 -0 Configuration t2g1eg0 t2g2eg0 t2g3eg0 t2g4eg0 t2g5eg0 t2g6eg0 t2g6eg1 t2g6eg2 t2g6eg3 t2g6eg4 CFSE Dq o -4 - 0.4 -8 - 0.8 - 12 - 1.2 - 16 - 1.6 - 20 - 2.0 - 24 - 2.4 - 18 - 1.8 - 12 - 1.2 -6 - 0.6 0 0

Configuration t2g1eg0 t2g2eg0 t2g3eg0 t2g3eg1 t2g3eg2 t2g4eg2 t2g5eg2 t2g6eg2 t2g6eg3 t2g6eg4

d1 d2 d3 d4 d5 d6 d7 d8 d9 d10