Methyl transfer from methylcobalamin to diaquocobinamide.

The transfer of the methyl group from methylcobalamin to diaquocobinamide in aqueous solution has been demonstrated by proton, carbon-13, and phosphorus-31 nuclear magnetic resonance spectroscopy. The products of this reaction are aquocobalamin and the methylaquocobinamides. Dicyanocobinamide and the cyanoaquocobinamides do not serve as methyl acceptors, while ligands such as pyridine and histidine reduce the rate of the transfer reactions. The methyl transfer is not affected by oxidizing agents such as O2, N2O, and H2O2, suggesting that the reaction does not involve free Co(I) or Co(II) corrinoids. The pH dependence of the rate of the transfer reaction from methylcobalamin to diaquocobinamide demonstrates that methylcobalamin in the "base-on" form and diaquocobinamide are the most effective methyl donor and acceptor, respectively. The most plausible mechanism for the transfer reaction involves the one-electron oxidation of methylcobalamin by diaquocobinamide to a methylcobalamin radical cation and cob(II)inamide. The very unstable methylcobalamin radical cation releases a methyl radical, which reacts with cob(II)inamide to generate the methylaquocobinamides.