Hydrophobic vitamin B12. II. Coordination geometry and redox behavior of heptamethyl cobyrinate in nonaqueous media.
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概要
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The nuclear cobalt(II) ion in heptamethyl cobyrinate iodide, Cob(II)ester·I, was found to assume a distorted square-planar geometry of Co–N<SUB>4</SUB> type with iodide as a counterion in a polar solvent (methanol) and a square-pyramidal one of Co–N<SUB>4</SUB>I type with the iodide ion coordinated at one of the axial positions in apolar solvents such as dichloromethane, benzene, and toluene. The redox chemistry of Cob(II)ester·I and heptamethyl cobyrinate perchlorate, [Cob(II)ester]ClO<SUB>4</SUB>, was investigated in various organic solvents by means of cyclic voltammetry and controlled-potential electrolysis. The Co(II)/Co(I) and Co(III)/Co(II) redox potentials for [Cob(II)ester]ClO<SUB>4</SUB> exhibited cathodic shifts as either solvent basicity or polarity was raised, and were found to be in the anodic side relative to the corresponding potentials for Co<SUP>II</SUP>(tpp) under identical conditions. The medium effect on the redox behavior of hydrophobic vitamin B<SUB>12</SUB> was discussed in connection with the microenvironmental effect on vitamin B<SUB>12</SUB> placed in the enzyme active sites.
- 公益社団法人 日本化学会の論文
著者
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Hisaeda Yoshio
Department Of Applied Chemistry Graduate School Of Engineering Kyushu University
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Murakami Yukito
Department Of Chemical Science And Technology Faculty Of Engineering Kyushu University
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Ohno Teruhisa
Department Of Applied Chemistry Faculty Of Engineering Kyushu Institute Of Technology
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Kajihara Akiro
Department of Organic Synthesis, Faculty of Engineering, Kyushu University
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