REACTION FIELD CREATED BY METAL COMPLEXES

本研究旨在建立金属配合物反应场的构建和修饰方法。在金属络合物上产生的反应场可以通过适当地改变配体来改变。十名研究人员在各个领域工作，被分为以下四组。高功能Monoclonal活性物质的创造Takashi ito，Kohtaro Osakada，and Sanshiro Komiya 2.空间和电子控制的多金属反应场的构建Hiroharu Suzuki，Kiyashi Isobe和Kazuyuki Tatsumi 3.高度可控的金属络合物反应场中有机底物的转化Tamotu Takahashi和Yasuo Wakatsuki 4.控制反应场的理论方法Nobuaki古贺和Shigeyoshi Sakaki第一组利用配位不饱和过渡金属络合物实现了CO_2、Si-C键和N-H键的活化。第二组发展了金属簇合物的系统合成方法。双核和三核钌多氢化物配合物可以活化包括烷烃在内的多种有机底物，并进行了前所未有的选择性C-H和C-C键断裂。系统地合成了一类具有Rh-S-W骨架的新型簇合物。第三类化合物进行了以锆环戊烯为合成中间体的新型有机转化反应和NO在六核羰基簇合物上的氧化还原反应。第四组对烯烃聚合和硅氢化反应等过渡金属配合物催化反应进行了从头算分子轨道研究。

This research project was intended to establish the methodology for the construction and modification of the reaction field of metal complex. The reaction field created on the metal complex can be modified by appropriately changing ligands. Ten researchers working in a variety of fields have been divided into the following four groups.1. Creation of Highly Functioned Mononuclear Active SpeciesTakashi ito, Kohtaro Osakada, and Sanshiro Komiya2. Construction of Sterically and Electronically Controlled Multimetallic Reaction FieldHiroharu Suzuki, Kiyashi Isobe, and Kazuyuki Tatsumi3. Conversion of Organic Substrates in the Highly Controlled Metal Complex Reaction FieldTamotu Takahashi and Yasuo Wakatsuki4.Theoretical Approach directed toward Control of Reaction FieldNobuaki Koga and Shigeyoshi SakakiThe first group achieved activation of CO_2, Si-C bond, and N-H bond by using coordinatively unsaturated transition metal complexes. The second group developed systematic synthetic method of metal cluster complexes. Di- and trinuclear polyhydride complexes of ruthenium could activate a variety of organic substrates including alkanes and unprecedented type of selective C-H and C-C bonds cleavage was performed. A new class of clusters with Rh-S-W framework were systematically synthesized. A novel organic transformation involving zirconacyclopentene as synthetic intermediate and redox reaction of NO on hexanuclear carbonyl clusters were performed by the third group. Ab initio MO studies of several transition metal complex-catalyzed reactions such as olefin polymerization and hydrosilation were done by the fourth group.