Abstract
Abstract The isomerization of cis-dichlorobis(ethylenediamine)cobalt(III) chloride to its trans form is induced at 0°C in methanol by ultraviolet irradiation. The visible light in the wavelength region of the ligand field bands is not effective, but the ultraviolet light corresponding to the charge transfer band is essential. The effects of the dissolved oxygen, the initial concentration of the reactant, and the intensity of the incident light were examined, and the reaction was found to proceed further even after the cessation of irradiation. A chain mechanism is proposed which includes the Co(II) species, the photoreduction product of the Co(III) complex, as a chain carrier. The isomerization reaction was also conducted at 0°C in the dark in the presence of cobalt(II) chloride and ethylenediamine; the most effective catalyst was assumed to be a five-coordinated Co(II) species, CoClen2+ . The induction period which was observed in the photoreaction was explained as being due to the deactivation of the reactive Co(II) species throguh oxidation with the dissolved oxygen.
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