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Dr. M. Gerken
Page71
Dr. M. Gerken
Page72
bonding, and the 2eg set is only weakly antibonding, and therefore, can be occupied without greatly perturbing the bonding.
Nevertheless, some of the most stable, unreactive metal complexes are indeed formed with metals having a d6 configuration. The
18-electron rule becomes particularly important for complexes with large ligand-field splitting.
8.2 Octahedral coordination complexes with -donor ligands.
So far, we have only considered -donor ligands (-bases). However, the metal t2g
orbitals have the correct symmetry for -bonding with ligand p orbitals, as shown
in the figure on the right-hand side. The SAOs with t2g symmetry are shown
below.
In the presence of p orbitals
(bonding orbitals) on the ligands a splitting of the t2g orbitals results, producing bonding and antibonding t2g sets that have filled
p orbitals The p orbitals on the ligand such as Cl-, Br-, H2O are filled and donate their electrons into the bonding t2g MO. The
formerly non-bonding metal t2g orbitals are elevated, effectively reducing the ligand-field splitting. In general -donor ligands (bases) will cause small ligand-field splitting, though they are quite strongly bonded to the metal centre.
Dr. M. Gerken
Page73