REACTION CONTROL OF ORGANOMETALLIC COMPLEXES RELEVANT TO CATALYTIC HYDROSILYLATION

催化氢化硅烷化相关有机金属配合物的反应控制

基本信息

批准号：
12450367
负责人：
OZAWA Fumiyuki
金额：
$ 5.7万
依托单位：
OSAKA CITY UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2000
资助国家：
日本
起止时间：
2000 至 2002
项目状态：
已结题

项目摘要

(1) All elementary processes responsible for ruthenium complex-catalyzed hydrosilylation of terminal alkynes have been identified by means of NMR analysis of catalytic solutions as well as model studies ofpresumed catalytic intermediates. The catalytic reactions yield (E)- and (Z)-alkenylsilanes, and relative ratio of these two stereoisomers of hydrosilylation products clearly depends on the reaction-courses of alkenylruthenium intermediates with hydrosilanes. Thus, there are two reaction-courses C-H bond formation with concomitant generation of a silylrutheinum intermediate via a sequence of oxidative addition and reductive elimination. Based on the mechanistic findings, highly efficient catalysts giving (E)- and (Z)-alkenylsilanes, independently, in 91-99% stereoselectivties have been developed. Catalytic performance of the newly developed catalysts has been demonstrated for stereocontrolled synthesis of (E)- and (Z)-rich poly (p-phenylenevinylene)s, which are highly expected electroptical materials(2) Novel palladium and platinum hydrides of rather unique catalytic properties have been prepared by the treatment of the methyl triflate complexes exhibit high catalytic activity for hydroamination of conjugated dienes, dehydrogenative silylation of ketones, and direct conversion of allylic alcohols(3) A variety of silylplatinum complexes have been prepared, and their reactivities toward C-Si reductive elimination and alkyne-insertion have been examined in detail by kinetic experiments. The silylplatinum complexes have been found to be highly reactive, as compared with the corresponding organoplatinum complexes having a platinum-carbon bond

（1）通过NMR分析催化溶液的NMR分析以及催化催化中间体的模型研究，已经鉴定出了终末炔烃的氢磷脂的所有基本过程。催化反应的产量（E） - 和（Z） - 烯基硅烷，以及这两种氢硅烷化产物的立体异构体的相对比显然取决于烷烯基硫硫代苯基中间体与氢硅烷的反应表。因此，有两种反应库C-H键的形成，并通过一系列氧化添加和还原性消除序列伴随着辅助生成。基于机械结果，已经开发了在91-99％的立体电位中给出（E） - 和（Z） - 金烯基硅烷的高效催化剂。已经证明了新开发的催化剂的催化性能是（E） - 和（Z） - 富集聚（P-苯基乙烯烯）S的立体对照合成，高度预期的电位材料（2）新颖的钯（2）新型钯和铂具有相当独特的催化剂的甲基甲基甲基甲基甲基甲基甲基甲基甲基甲基甲基化型的耐药性，以甲基三甲基的催化剂进行处理。共轭二烯，酮的脱氢作用以及烯丙基醇的直接转化（3）已经制备了各种硅藻土复合物，并且通过动力学实验详细检查了它们对C-SI减少消除和藻类插入的反应性。与具有铂 - 碳键的相应有机晶酸复合物相比