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首页> 外文期刊>Bulletin of the Chemical Society of Japan >Hydrophobic Vitamin B_12.Part 20:# Supernucleophilicity of Co(I) Heptamethyl Cobyrinate toward Various Organic Halides
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Hydrophobic Vitamin B_12.Part 20:# Supernucleophilicity of Co(I) Heptamethyl Cobyrinate toward Various Organic Halides

机译：疏水性维生素B_12。第20部分：＃Co（I）邻苯二甲酸钴甲酯对各种有机卤化物的超亲核性

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摘要

Heptamethyl cobyrinate,hydrophobic vitamin B_12,was reduced to its Co(I) species by a reaction with sodium tet-rahydroborate,which reacted with various organic halides,such as CH_2C1_2,CHC1_3,CC1_4,CHBrCl_2,CHBr_3,CC1_3CH_3,CFCl_3,and BrCH_2CH_2CH_3,to form the corresponding alkylated complexes with dehalogenation.The alkylated complexes were characterized by elemental analyses and ESI-MS,and the photo-lability of the alkylated complexes was confirmed by the UV-vis absorption spectral change.The fashion for cleavage of the cobalt-carbon bond under irradiation with visible light was investigated by an ESR spin-trapping technique.The redox behavior of a series of alkylated complexes was investigated by cyclic voltammetry.The alkylated complexes showed an irreversible reduction peak at -1.21 to -1.29 V vs Ag-AgCl,which showed cleavage of the cobalt-carbon bond by electrolysis.
机译：通过与四氢硼酸钠（与四有机硼化物，例如CH_2C1_2，CHC1_3，CC1_4，CHBrCl_2，CHBr_3，CC1_3CH_3，CFCl_3和BrCH_2）反应的四甲基硼氢化钠反应，将庚二酸七甲酯疏水的维生素B_12还原为其Co（I）物种。通过元素分析和ESI-MS对烷基化的配合物进行表征，并通过紫外可见吸收光谱的变化证实了烷基化的配合物的光不稳定性。用ESR自旋阱技术研究了可见光照射下的碳键，通过循环伏安法研究了一系列烷基化配合物的氧化还原行为，烷基化配合物在-1.21至-1.29 V处相对于Ag具有不可逆的还原峰-AgCl，其显示通过电解裂解钴-碳键。

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