Transition metal complexes are often colored due to d-d electronic transitions within the metal ion. Crystal field theory explains how ligands cause the degeneracy of the metal's d-orbitals to be lifted, splitting them into lower energy t2g and higher energy eg sets. In an octahedral complex, the eg orbitals are raised 0.6Δo above the average energy level and the t2g orbitals are lowered 0.4Δo, accounting for the absorption spectra observed. Transition metals also catalyze reactions due to their ability to adopt multiple oxidation states and form surface complexes that weaken reactant bonds.
Transition metal complexes are often colored due to d-d electronic transitions within the metal ion. Crystal field theory explains how ligands cause the degeneracy of the metal's d-orbitals to be lifted, splitting them into lower energy t2g and higher energy eg sets. In an octahedral complex, the eg orbitals are raised 0.6Δo above the average energy level and the t2g orbitals are lowered 0.4Δo, accounting for the absorption spectra observed. Transition metals also catalyze reactions due to their ability to adopt multiple oxidation states and form surface complexes that weaken reactant bonds.
Transition metal complexes are often colored due to d-d electronic transitions within the metal ion. Crystal field theory explains how ligands cause the degeneracy of the metal's d-orbitals to be lifted, splitting them into lower energy t2g and higher energy eg sets. In an octahedral complex, the eg orbitals are raised 0.6Δo above the average energy level and the t2g orbitals are lowered 0.4Δo, accounting for the absorption spectra observed. Transition metals also catalyze reactions due to their ability to adopt multiple oxidation states and form surface complexes that weaken reactant bonds.
Transition metal complexes are often colored due to d-d electronic transitions within the metal ion. Crystal field theory explains how ligands cause the degeneracy of the metal's d-orbitals to be lifted, splitting them into lower energy t2g and higher energy eg sets. In an octahedral complex, the eg orbitals are raised 0.6Δo above the average energy level and the t2g orbitals are lowered 0.4Δo, accounting for the absorption spectra observed. Transition metals also catalyze reactions due to their ability to adopt multiple oxidation states and form surface complexes that weaken reactant bonds.
# d-orbitals in complex ions for octahedral complex (Simple
explanation by crystal field theory)
* Crystal Field Theory (CFT) This theory was developed by Bethe and Van Vleck and was mainly applied to ionic crystals, which is called crystal field. This theory has been proved to be successful in explaining stereochemistry, reaction paths, magnetic properties, absorption spectra, and thermodynamic properties of several complexes.
The following are the basic assumptions/postulates of CFT: 1.
Ligands are treated as point charges or point dipoles. 2. The bonding between the metal cation and ligand is electrostatic in origin. There is no interaction between metal orbital and ligand orbital. 3. The d-orbitals on the metal have the same energy (degenerate). However, when a complex is formed, the ligands destroy the degeneracy of d-orbitals i.e., the orbitals now have different energies.
The interaction between the electrons of cation and those of ligands
isresponsible for the splitting of the orbitals of the metal cation. This splitting of five degenerate d-orbitals of the metal ion into two sets of d-orbitals with different energies is called crystal field splitting. The two sets of d-orbitals i.e., dxy, dyz, and dxz commonly known as t2g (triply degenerated) and dx2- y2and dz2, commonly known as eg (doubly degenerated). There occurs repulsion between electrons in metal d-orbitals and electrons of ligands. Such repulsion is more when metal d-orbitals are directed toward the ligands that when it is away from the ligand. Thus, dx2- y2and dz2 orbitals that are directed towards the x, y, and z axes, experience more repulsion, and energy is raised. The dxy, dyz, and dxz orbitals that lie in between axes will be lowered in energy relative to average energy in the crystal field. The energy difference between eg and t2g set of orbitals is measured in terms of parameter Δo or 10 Dq, known as Crystal Field Stabilization Energy (CFSE). In an octahedral field, the eg orbitals are 0.6Δo (6Dq) above the average energy level (baricentre) and t2g orbitals are 0.4Δo (4Dq) below the baricentre. Hence, the total increase in energy of four eg electrons is equal to the total decrease in energy of six t2g electrons, preserving the centre of gravity. # Reason for the colour of transition metal compounds 1. Incompletely filled d-shell (d-d transition) Transition metal complexes are mostly coloured due to the presence of unpaired electrons or incomplete filling of d-orbitals where absorption of light could lead to a d-d electronic transition from the visible region.
During the process of absorption of light, the electrons of transition metal
ions get excited from low energy d-level to high energy d-level. The Colour of the companion ion can be explained with the help of CFT. 2. Polarisation A cation polarizes the anions. It means, the cation distorts the electron cloud and implies a greater covalent contribution. The colour arises because of polarization. For example, the Ag+ion polarizes the halide ions (Br –and I -). The AgBr is pale yellow and AgI is yellow due to polarization. 3. By charge transfer In the case of MnO4-, an electron is momentarily transferred from oxygen to metal and momentarily changes O2-to O and reduces the oxidation state of metal from Mn7+ to Mn6+. Charge transfer requires the energy levels of the two different atoms in a fairly close state. Charge transfer always produces a very intense colour like KMnO4 in solution is intensely purple. # Catalytic Properties of Transition Metals The main reasons for the catalytic activity of transition metals are the ability to adopt multiple oxidation states and form complexes. In other cases, the solid surface of transition metal provides surface area for the formation of bonds between reactant molecules and atoms. This increases the concentration of reactant molecules on the surface of the catalyst and weakens the bond of the reactant.