REACTION CONTROL OF ORGANOMETALLIC COMPLEXES RELEVANT TO CATALYTIC HYDROSILYLATION

(1)通过对催化溶液的核磁共振分析以及对假定的催化中间体的模型研究，确定了钌络合物催化末端炔的硅氢化的所有基本过程。催化反应生成(E)-和(Z)-烯基硅烷，而这两种硅氢化产物的立体异构体的相对比例明显取决于烯基钌中间体与氢硅烷的反应过程。因此，有两个反应过程——C-H键的形成伴随着通过一系列氧化加成和还原消除产生的硅钌中间体。在此基础上，开发出了具有91-99%立体选择性的(E)-和(Z)-烯基硅烷的高效催化剂。新开发的催化剂在立体控制合成富(E)-和(Z)-的聚（对苯乙烯）烯方面的催化性能得到了证明。(2)三氟酸甲酯配合物制备了具有独特催化性能的新型钯和铂氢化物，对共轭二烯的氢胺化、酮的脱氢硅基化、(3)制备了多种硅铂配合物，并通过动力学实验对其C-Si还原消除反应和炔插入反应进行了详细的研究。与相应的具有铂碳键的有机铂配合物相比，硅铂配合物具有高活性

(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