Redox Behavior of Simple Vitamin B12 Model Complexes and Electrochemical Catalysis of Carbon-Skeleton Rearrangements

Article abstract of DOI:10.1246/bcsj.62.2219

Various cobalt complexes of 4,10-dipropyl-5,9-diazatrideca-4,9-diene-3,10-dione dioxime, (C2C3)(DOH)2pn, were prepared, and redox behavior of them was investigated by means of cyclic voltammetry; Co(II)/Co(I) redox potentials in the range of -0.69 through -0.7 V vs.Ag/AgCl.The monomethylated complex, which has a cobalt-carbon bond at one axial site of the nuclear cobalt, was disproportionated to the dimethylated complex, involving two cobalt-carbon bonds at both axial sites, and the Co^I species by one-electron reduction.The dimethylated complex was inactive for electrochemical reduction, but transformed into the monomethylated complex via cleavage of a cobalt-carbon bond upon electrochemical oxidation.The electrolyses of 1-bromo-2,2-bis(ethoxycarbonyl)propane, 1-bromo-2-cyano-2-ethoxycarbonylpropane, and 2-acetyl-1-bromo-2-ethoxycarbonylpropane in the presence of III<(C2C3)(DO)(DOH)pn>Br2> in N,N-dimethylformamide did not proceed in a divided cell at -2.0 vs.Ag/AgCl, since the corresponding dialkylated complexes, inactive for electrochemical reduction, were formed in the course of reaction.When imidazole was added to solutions for the electrolysis, the reaction proceeded efficiently by the trans effect arising from the coordinated axial base and the corresponding carbon-skeleton rearrangement products were obtained.On the other hand, the carbon-skeleton rearrangement proceeded in an undivided cell even in the absence of imidazole; the dialkylated complex was decomposed to give the monoalkylated complex and the reduction and rearrangement products by electrochemical ocxidation on the anode.