New Development of Electron Transfer in Co-ordination Compounds

该小组的研究人员扩展了过渡金属配位化合物和有机化合物与金属或低价金属盐的组合中的电子转移过程的研究。这些研究在有机电化学、电生物化学、有机化学、生物化学和有机合成中具有重要意义。在这次有机电化学优先领域的科学研究期间，该小组的研究人员取得了以下成果：1.电子转移过程和产生的活性物种的使用：在有机电化学的一个元素过程中，电子从金属到有机化合物的转移。已经发展了两个与电子从金属到有机卤化物的受控转移有关的反应。一种是立体控制反应，在手性醛的存在下，1，1-二卤代烷对映体选择性地生成手性构筑块。这一新工艺将提供新的不对称合成…更多的是各种有机化合物。第二种是从金属到二卤化物的选择性电子转移，由另一种金属介导或催化。二碘甲烷与纯锌反应，以极高的产率得到碘甲基锌，不能检测到双(碘多硫)甲烷的生成。与纯锌反应不同，二碘甲烷与含铅催化量的锌反应只生成双碘甲烷。用含铅的锌或纯锌的混合物与PbCl2的催化量反应生成双碘甲基锌甲烷，表明电子向碘甲基碘化锌的转移是由铅催化剂控制的。2.新的电子转移体系的构建：人们广泛地研究了新的电子转移体系，以利用有机部分从配位化合物到底物的选择性电子转移和非对映选择性转移产生的反应物种来发展高选择性的反应。3.生化作用中的电子转移过程：生物活性的电化学发光探测已经得到了广泛的研究。利用该方法对DNA偶联的抗肿瘤和抗病毒药物进行了表征。应用该方法对抗体进行了识别研究。较少

Investigators of this group extended the research on electron transfer processes in transition metal coordination compounds and combination of organic compounds and metal or low-valent metal salts. These research are fundamentally important in organic electrochemistry, electrobiochemistry, organic chemistry, biochemistry, and organic synthesis. In the period of this Scientific Research on Priority Areas of Organic Electrochemistry, the investigators of the group produced the followihg results.1.Studies on Electron Transfer Process and Use of Generated Reactive Species : Electron transfer from metal to organic compounds in an elemental process in organic electrochemistry. Two reactions related to controlled electron transfer from metal to organic halides have been developed. One is stereocontrolled reaction containing enantioselective generation of chiral building block from 1,1-dihaloalkanes in the presence of chiral aldehydes. This novel process would provide new asymmetric synthesis … More of various organic compounds. Second one is selective electron transfer to dihalides from metal mediated or catalyzed by another metal. Diiodomethane reacted with pure zinc to give iodomethylzinc iodide in excellent yield ; formation of dimetallic species, bis (iodozincio) methane, could not be detected. In contrast to the reaction using pure zinc, treatment of diiodomethane with zinc containing catalytic amount of lead afforded bis (iodozincio) methane exclusively. Formation of bis (iodozincio) methane from iodomethylzinc iodide by treatment with zinc containing lead or a mixture of pure zinc and catalytic amount of PbCl_2 suggested that electron transfer to iodomethylzinc iodide was controlled by lead catalyst.2.Construction of New Electron Transfer System : New electron transfer systems have been extensively studies in order to develop highly selective reactions using reactive species generated by selective electron transfer and diastereoselective transfer of organic moieties from coordination compounds to substrates. Some successful results were obtained using modified Vitamin B_<12>.3.Electron Transfer Process in Biochemical Interaction : Electrochemical luminescence probing of biological activities have been extensively studied. DNA-interfacing antitumor and antiviral agents were characterized by using this process. Antibody recognition was also studied by applying the method. Less