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Dalton Transactions

The international journal for inorganic, organometallic and bioinorganic chemistry



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Dalton Trans., 2009, 9898 - 9905, DOI: 10.1039/b909163g

Vitamin B12 model complex catalyzed methyl transfer reaction to alkylthiol under electrochemical conditions with sacrificial electrode

Ling Pan, Hisashi Shimakoshi, Takahiro Masuko and Yoshio Hisaeda

Catalytic methyl transfer reactions from methyl tosylate to 1-octanethiol catalyzed by heptamethyl cobyrinate perchlorate, [Cob(II)7C1ester]ClO4, were investigated under electrochemical conditions. As a model study for the cobalamin-dependent methyl transfer reaction from methyltetrahydrofolate to homocysteine, controlled-potential electrolyses were carried out at -1.0 V vs. Ag/AgCl using a zinc plate as the sacrificial anode at 50 °C in the dark. A turnover behaviour for the methyl transfer reaction was observed for the first time under non-enzymatic reaction conditions. Co(I) species, which is generated from the continuous electrolysis of [Cob(II)7C1ester]ClO4, and its methylated CH3-Co complex were found to be important intermediates. The mechanism for such a methyl transfer reaction was investigated by product analysis, electronic spectroscopy and ESR spin-trapping experiments. A simple vitamin B12 model complex was also utilized as the catalyst for the methyl transfer reaction.

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