Reduction of cobalt(III) complexes by intramolecular electron transfer from bound free radicals

The specific rates of reduction of [Co(NH3)6]3+ by a series of nitrobenzoate and nitrogen heteroaromatic anion radicals are reported. The rates of intramolecular electron transfer from the same anion radicals to a central cobalt(III) bound to them via a carboxylate group are reported, as well as for some pyrazine carboxylate anion radicals bound to the cobalt via the carboxylate and the N1 atom. The factors affecting the rate of intramolecular electron-transfer processes are discussed in detail. (author)