Redox Behavior of Simple Vitamin B<sub>12</sub>Model Complexes and Electrochemical Catalysis of Carbon-Skeleton Rearrangements
作者:Yukito Murakami、Yoshio Hisaeda、Sheng-Di Fan、Yoshihisa Matsuda
DOI:10.1246/bcsj.62.2219
日期:1989.7
to the dimethylated complex, involving two cobalt–carbon bonds at both axial sites, and the CoI 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
制备了 4,10-dipropyl-5,9-diazatrideca-4,9-diene-3,10-dione dioxime, (C2C3)(DOH)2pn 的各种钴配合物,并通过以下方法研究了它们的氧化还原行为循环伏安法;Co(II)/Co(I) 氧化还原电位在 -0.69 到 -0.7 V 范围内,与 Ag/AgCl 相比。在核钴的一个轴向位点具有钴-碳键的单甲基化配合物与二甲基化配合物不成比例,在两个轴向位点都涉及两个钴-碳键,并且 CoI 物种通过单电子还原。二甲基化配合物对电化学还原没有活性,但通过电化学氧化时钴-碳键的断裂转化为单甲基化配合物。1-溴-2,2-双(乙氧基羰基)丙烷、1-溴-2-氰基-2-乙氧基羰基丙烷的电解,