화학공학소재연구정보센터
Inorganic Chemistry, Vol.42, No.13, 4018-4028, 2003
Two-electron-transfer redox systems, Part 7: Two-step electrochemical oxidation of the boron subhalide cluster dianions B6X62- (X=Cl, Br, I)
Boron subhalide cluster dianions B6X62- (X = Cl, Br, I) are electrochemically oxidized in two steps. According to cyclic voltammograms, the first step is chemically reversible and yields the corresponding radical anions B6X6.-. The electron transfer is nearly diffusion controlled. The second, slower electron-transfer step leads to a species which we assume to be the hitherto not yet described neutral compounds B6X60. The voltammograms indicate a coupled fast catalytic reaction, producing the radical anions in a reduction by an electrolyte component. Computer simulations of the cyclic voltammograms reveal mechanistic details of the redox reactions, as well as quantitative values for formal potentials, rate constants, and diffusion coefficients. The results are compared to other BnXn redox systems.