Abstract
cis-[Co(III)(en)2PVICl]Cl2, cis-[Co(III)(en)2NEICl]Cl2 (PVI:poly-(1-vinyl-2-methylimidazole), Pn=250, NEI: N-ethylimidazole) complexes were synthesized and the reduction of these complexes by FeEDTA2- was investigated. Especially, the effects of ionic strength and the addition of alcohdls were examined and the activation parameters (ΔF, ΔH, ΔS ) were measured.With an increase in the ionic strength μ, log k (k: the pseudo first order rateconstant of the electron-transfer reaction) decreased linearly in relation to μ in the Co(III)-PVI system. It was noticed clearly from the result of the viscosity measurement that the conformational changes of the polymer complex gave a large influence on the reactivity. Furthermore, in the H2O-alcohol mixed solvent, an increase in the alcohol concentration accelerated the reaction and, when ethanol or 2-propanol was used in the Co(III)-PVI system, the maximum of k was observed. With a rise of the reaction temperature, the maximum point was shifted to the lower alcohol concentration. These phenomena were discussed in regard to the conformational changes of the polymer complex.
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