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Electronic state of metal complexes and dynamics of their electron transfer reactions

金属配合物的电子态及其电子转移反应的动力学

基本信息

批准号：
03303005
负责人：
OGINO Hiroshi
金额：
$ 4.48万
依托单位：
TOHOKU UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Co-operative Research (A)
财政年份：
1991
资助国家：
日本
起止时间：
1991 至 1992
项目状态：
已结题

项目摘要

A great progress was achieved for the synthesis of monomeric,dimeric,and polymeric metal complexes as well as metal clusters. Especially for several series of dimeric complexes, rational syntheses have became possible.On the basis of these synthetic results,the relation between electronic state of complexes and their redox potentials was investigated. Various novel electron transfer systems were discovered:System which generates mixed valence states accompanying with redox processes,electron transfer kinetics which obeys zero-th order rate law,electron transfer system which couples with proton transfer,and system which catalyzes the reduction of CO_2. Photo-induced electron transfer reactions of metal complexes were extensively investigated from both theoretical and experimental points of view. Structural analysis of chemical species produced on electrode surface was carried out with the aid of scanning tunneling microscope and provided useful information for the electron transfer at electrode-solution interface.These investigations were carried out by cooperative researches. Two symposia were held on November 11 and 12,1991(Tokyo)and November 11 and 12,1992(Okazaki) for discussing the results and exchanging ideas.We believe that our cooperative research was undertaken quite timely,since 1992 Nobel prize was awarded to Professor R.A.Marcus who made a great contribution on electron transfer theory in chemical system.

在单体、二聚、聚合金属配合物以及金属簇的合成方面取得了重大进展。特别是对于几个系列的二聚配合物，合理的合成成为可能。在这些合成结果的基础上，研究了配合物的电子态与其氧化还原电位之间的关系。发现了各种新型电子传递体系：伴随氧化还原过程产生混合价态的体系、服从零级速率定律的电子传递动力学体系、与质子传递耦合的电子传递体系、催化CO_2还原的体系。从理论和实验的角度对金属配合物的光诱导电子转移反应进行了广泛的研究。借助扫描隧道显微镜对电极表面产生的化学物质进行了结构分析，为电极-溶液界面的电子转移提供了有用的信息。这些研究是通过合作研究进行的。 1991年11月11日至12日（东京）和1992年11月11日至12日（冈崎）分别召开了两次研讨会，对成果进行了讨论和交流。我们认为，我们的合作研究进行得很及时，自1992年诺贝尔奖授予R.A.Marcus教授以来，他在化学体系电子转移理论方面做出了巨大贡献。