Coenzyme AdoB12 vs AdoB12.-homolytic Co-C cleavage following electron transfer: a rate enhancement greater than or equal to 10(12)

Abstract

Comparison of the 25 degrees C Co-C bond homolysis rate constant of adenosyl-cobalamin (coenzyme B12) vs that for electrochemically reduced adenosyl-cobalamin radical anion indicates a rate enhancement of at least 10(12 +/- 2) upon the addition of one antibonding electron. Even though electrochemical reduction promotes Co-C homolysis by virtually the same amount as the 10(12 +/- 1) enzymic activation seen for adenosylcobalamin, electron-transfer activation of the Co-C homolysis in adenosylcobalamin-dependent enzyme reactions is considered unlikely, based on four lines of evidence.