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

多核过渡金属配合物与有机金属聚合物及相关反应的实用催化过程探索

基本信息

批准号：
17350050
负责人：
NAGASHIMA Hideo
金额：
$ 9.65万
依托单位：
Kyushu University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2005
资助国家：
日本
起止时间：
2005 至 2007
项目状态：
已结题

项目摘要

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

使用有机金属前体的分子催化剂是现代有机和聚合物合成的最重要工具之一。最近保护全球环境的要求促使开发可重复使用的分子催化剂，该催化剂不会将金属残留物浸出到产品中。使用聚合有机金属试剂进行催化反应，可将有机金属物质固定在聚合物基质中，以便在反应后轻松从产物中去除。多核有机金属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）催化剂设计和合成，（b）分子结构和电子结构分析，（c）催化反应。非聚合试剂，(d) 与聚合试剂的催化反应该项目首先关注羧基酰胺的催化还原。三钌羰基簇，(μ_3，η_2，η_3，η_5-苊基)Ru_3(CO)7，被证明是为此目的最活跃和通用的催化剂之一，可以顺利地将仲酰胺和叔酰胺转化为相应的催化剂。在某些条件下，甲酰胺的还原过程中，聚甲基氢硅氧烷（PMHS）的应用仍保持完整。还原剂形成硅氧烷凝胶，所有催化物质都被吸收，含有金属物质的凝胶可以很容易地从产品中去除，并可作为催化剂重复使用。该结果在 PMHS 的酰胺催化还原中得到了扩展。使用其他分子催化剂，提供铂催化的胺的形成和铱催化的有机铝聚合物的生产，甲基铝氧烷(MAO)是一种著名的催化烯烃聚合助催化剂。我们对异氰化物有机镍配合物和早晚期杂双金属配合物两种类型的有机金属化合物进行了催化剂设计，并对其在MAO存在下的乙烯聚合进行了研究。对硅氧烷或铝氧烷基质中的金属物质进行了较少的研究。