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

• 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
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-12450367/
• 关键词: Ruthenium Complexes; Platinum Complexes; Catalytic Hydrosilylation; Dehydrogenative Silylation; Catalytic Mechanisms; Stereoselective Reactions; o-Bond Metathesis; Reductive Elimination; ヒドロシリル触媒反応; ルテニウム触媒; 立体選択性; ポリフェニレンビニレン; sp^2混成リン配位子; 酸

(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)通过对催化溶液的核磁共振分析和对可能的催化中间体的模型研究，确定了催化末端炔氢硅氢化反应的所有基本过程。催化反应生成(E)-和(Z)-烯基硅烷，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Ru中间体与氢硅烷的反应历程。因此，有两个反应过程-C-H键的形成，同时通过一系列氧化加成和还原消除生成硅基Rutheine中间体。基于这一机理发现，已开发出分别给出(E)和(Z)-烯基硅烷的高效催化剂，其立体选择性分别为91-99%。新开发的催化剂对高(E)和(Z)富聚对苯乙叉S的立体控制合成具有良好的催化性能。(2)通过对三氟酸甲酯的处理，制备了具有独特催化性能的新型钯和铂氢化物。它们对共轭双烯的氢胺化、酮的脱氢硅基化和烯丙醇的直接转化具有较高的催化活性。与相应的具有铂-碳键的有机铂配合物相比，已发现硅基铂配合物具有高活性

项目成果

丸山洋一郎: "Mechanisms of C-Si and C-H Bond Formation on the Reactions of Alkenylruthenium (II) Complexes with Hydrosilanes"Organometallics. 19・7. 1308-1318 (2000)

丸山洋一郎：“烯基钌 (II) 配合物与氢硅烷反应的 C-Si 和 C-H 键形成机制”有机金属学 19・7 (2000)。