Exploration of Practical Catalytic Processes by Virtue of Multinucjear Transition Metal Complexes Associated with Organometallic Polymers and Related Reactions

以有机金属为前驱体的分子催化剂是现代有机合成和高分子合成的重要工具之一。近年来，全球环境保护的要求迫切要求开发可重复使用的分子催化剂，这些分子催化剂不会将金属残留物浸出到产品中。本研究涉及使用高分子有机金属试剂的催化反应，这是有用的固定在聚合物基体中的有机金属物种，反应后从产物中容易地去除。我们感兴趣的是双核和多核的有机金属簇作为一个潜在的预催化剂，而有机硅氧烷和铝氧烷作为一个合适的有机金属聚合物。本研究包括四个步骤：（a）催化剂的设计与合成，（B）分子结构和电子结构的分析，（c）非聚合试剂的催化反应，（d）聚合试剂的催化反应。该项目首先集中在催化还原carbox ...更多信息 （μ_3，η_2，η_3，η_5-苊烯）Ru_3（CO）_7是一种活性最高、用途最广的催化剂。仲酰胺和叔酰胺以高产率顺利转化为相应的胺。在某些条件下，甲酰胺的还原在其他官能团保持完整的情况下进行。聚甲基氢硅氧烷（PMHS）作为还原剂的应用结果在硅氧烷凝胶的形成，其中所有的催化物种被吸收。含有金属物质的凝胶可容易地从产物中除去，并可作为催化剂重复使用。结果扩大了在催化还原酰胺与PMHS使用其他分子催化剂，提供铂催化形成胺和铱催化生产的敌人。有机铝聚合物甲基铝氧烷（MAO）是一种著名的烯烃聚合助催化剂。设计了两种类型的有机金属化合物催化剂，即异腈衍生的有机镍配合物和早-晚杂环化合物，并进行了在MAO存在下的乙烯聚合的研究。研究了硅氧烷或铝氧烷基质中的金属物种。少

Molecular catalysts using organometallic precursors are one of the most important tools for modern organic and polymer synthesis. Recent requirement for protection of global environment urges to develop reusable molecular catalysts, which do not leach the metallic residues to the product. The present research deals with the catalytic reactions using the polymeric organometallic reagents, which are useful for fixing the organometallic species in the polymer matrix for facile removal from the product after the reaction. We are interested in di- and polynuclear organometallic clusters as a potential precatalyst, whereas organosiloxanes and aluminoxanes as a suitable organometallic polymers. The research consists of four steps, (a) catalyst design and synthesis, (b) analysis of molecular structures and electronic structures, (c)catalytic reactions with non-polymeric reagents, (d) catalytic reactions with polymeric reagents. The project was first focused on the catalytic reduction of carbox … More amides with a triruthenium carbonyl cluster, (μ_3, η_2, η_3, η_5-acenaphthylene)Ru_3(CO)7, which is proved to be the one of the most active and versatile catalysts for this purpose. Secondary and tertiary amides are smoothly converted to the corresponding amines in high yields. Under certain conditions, the reduction of carboxamides proceeds with the other functional groups remaining intact. Application of polymethylhydrosiloxane (PMHS) as the reducing reagent results in formation of siloxane gel, to which all of the catalytic species are soaked up. The gel containing metallic species is facilely removable from the product, and reusable as the catalyst. The results were expanded in catalytic reduction of amides with PMHS using other molecular catalysts, providing platinum-catalyzed formation of amines and iridium-catalyzed production of enemies. Organoaluminium polymer, methylaluminoxane(MAO), is a famous cocatalyst for catalytic olefin polymerization. Catalyst design of two types of organometallic compounds, organonickel complexes derived from isocyanides and early-late heterobimetallic complexes, was achieved and subjected to studies on the ethylene polymerization in the presence of MAO. The metallic species in the siloxane or aluminoxane matrix was investigated. Less