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The electro-reduction of a series of Co(III) complexes of the type cis-β -[Co(trien)(4-R-Py)Cl]Cl 2 , where trien = triethylenetetramine and R = H, Me, Et, t-Bu, COMe, and CN, has been studied in propan-2-ol/water and 1,4-dioxane/water binary mixtures. The redox potential (E 1/2 ) data were correlated with solvent and structural parameters with an aim to shed some light on the mechanism of these reactions. Correlation of E 1/2  with macroscopic solvent parameters indicated that the reactivity is influenced by both specific and non-specific solute-solvent interactions. The reduction of Co(III) to Co(II) in these complexes was observed to become increasingly easier with an increase in the dipolarity/ polarizability of the medium as evidenced by the Kamlet-Taft correlation. The difference in the relative lenience of the reduction has been explained using the difference in H-bonding properties of the medium.

zeitschrift für naturforschung b

Differential Pulse Voltammetric Studies of Some Mixed-ligand Co(III) Complexes in Aquo-Organic Solvent Media Possessing Different Hydrogen Bonding Properties