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Electron transfer: 150. The reaction of corrin-bound cobalt(III) with indium(I) — an additional mechanistic variation

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(Corrin)cobalt(III) is reduced by indium(I) to its Co(II) counterpart (cob(II)alamin, B12r) at pH 1-2 in aqueous chloride. In these solutions the aqua oxidant (B12a) is in mobile anation equilibrium with its chloro derivative. At [Cl] ⩿ 0.03 M, consumption of Co(III) is exponential and proceeds by parallel paths involving the aqua- and chloro-substituted oxidants. At [Cl]  0.10 M, rates are governed mainly by an preliminary act requiring In(I) and 2 Cl, but no Co(III). This initiation step generates a more reactive In(I) species which is taken to result from a slow heterolysis and loss of ligating water from InCl2(aq).


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