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

金属单体、二聚体和聚合物配合物以及金属簇的合成取得了很大进展。特别是对一些系列的二聚体配合物，合理的合成已成为可能。在这些综合结果的基础上，研究了配合物的电子态与其氧化还原电位的关系。发现了多种新型的电子传递体系：伴随氧化还原过程产生混合价态的电子传递体系、服从零阶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还原的电子传递体系。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。利用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-溶液界面的电子传递提供了有用的信息。这些调查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）分别举行了两次专题讨论会，讨论成果和交换意见。我们认为我们的合作研究是非常及时的，因为1992年诺贝尔奖授予了r.a.m umarcus教授，他在化学系统的电子传递理论方面做出了巨大的贡献。

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.