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

有机金属前体分子催化剂是现代有机高分子合成的重要工具之一。近年来，保护地球环境的要求促使人们开发可重复使用的分子催化剂，这种催化剂不会将金属残留物浸出到产品中。本研究的目的是利用聚合金属有机试剂进行催化反应，将金属有机物质固定在聚合物基体上，使反应后的产物易于去除。我们感兴趣的是双核和多核有机金属团簇作为潜在的预催化剂，而有机硅氧烷和铝氧烷作为合适的有机金属聚合物。该研究包括四个步骤，(a)催化剂设计与合成，(b)分子结构和电子结构分析，(c)与非聚合试剂的催化反应，(d)与聚合试剂的催化反应。本课题首先研究了三钌羰基簇（μ_3, η_2, η_3， η_5-苊）Ru_3(CO)7对carbox…More酰胺类化合物的催化还原反应，并证明了该催化剂是催化还原活性最高、用途最广的催化剂之一。仲胺和叔胺可以顺利地高收率地转化为相应的胺。在一定条件下，羧胺的还原过程中其他官能团保持完整。采用聚甲基氢硅氧烷（PMHS）作为还原剂，形成硅氧烷凝胶，吸收了所有的催化物质。含有金属的凝胶很容易从产品中去除，并可作为催化剂重复使用。该结果在PMHS催化还原酰胺的应用中得到扩展，使用其他分子催化剂，提供铂催化形成胺和铱催化产生敌人。有机铝聚合物甲基铝氧烷（MAO）是一种著名的催化烯烃聚合的助催化剂。设计了两类金属有机化合物的催化剂，即异氰酸酯衍生的有机镍配合物和早-晚杂双金属配合物，并对MAO存在下的乙烯聚合进行了研究。研究了硅氧烷和铝氧烷基体中的金属形态。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