The object of this project has been to study the vicinal effect and the related conformational effect which define the optical activity induced in the d-d transitions of metal complexes by coordination of unidentate and bidentate asymmetric ligands. This investigation has been approached from an empirical viewpoint, involving the preparation and investigation by circular dichroism (CD) and other spectroscopic techniques of series of cobalt(III) complexes of asymmetric ligands. Two series of pentaamminecobalt(III) complexes of asymmetric α-substituted carboxylic acids were prepared with coordinated unidentate L-(2-substituted)propionates and N,N-dimethyl- L-α-aminocarboxylates. The solution CD of these complexes were measured in various aqueous environments, as well as the variable temperature and variable solvent CD of several selected complexes. From low-temperature CD studies, the importance of conformational equilibria in determining the observed CD became apparent. The observed CD of these complexes can be interpreted in terms of two oppositely-signed separate conformer Cotton effects 1E(+) and 1E(-), the resultant CD in any environment being dependent on the mole fractions of the two dominant conformers. A series of pentaamminecobalt(III) complexes of asymmetric unidentate (1-substituted)ethylamines was prepared, and their solution CD measured. The size of the observed rotational strength was found to be related to the bulk of the substituent group. Variable temperature CD and variable solvent CD and proton magnetic resonance (PMR) spectra were measured for selected complexes. It appears that asymmetric salvation of the amine donor group may play a part in determining the observed rotational strength in these complexes. Tetraamminecobalt(III) complexes of several bidentate asymmetric 2-aminoalcohols and α-hydroxycarboxylates were prepared and their aqueous CD spectra investigated. The 2-aminoalcohols and α-hydroxycarboxylates are the oxygen analogues of 1 ,2-diamines and α-aminocarboxylates respectively, and the observed CD spectra of complexes of all four types of ligands were measured. The CD of the ligands with OH donor groups were found to be markedly dependent on the pH of the solution and on deprotonation of this OH group. Variations in the CD spectra of selected complexes with temperature were related to conformational preferences in the chelate rings. Investigation of the CD spectra of cobalt(III) complexes of bidentate asymmetric diamines with alkyl substituents indicated that the conformational effect is the dominant source of optical activity in these complexes. Small variations in the observed rotational strength of the tetraamminecobalt(III) complexes of R-1,2-propanediamine and R,R-1,2-cyclohexanediamine with temperature are consistent with the existance of one dominant conformation in these chelate rings. Variable solvent CD and PMR investigations of trans-dichlorobis(R-1,2-propanediamine)cobalt(III) chloride and the related diammine complex indicated that asymmetric salvation of the non-equivalent protons of the amine donor groups is a source of optical activity in complexes with five-membered diamine chelate rings. …