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)钌络合物催化的末端炔硅氢化反应的所有基本过程已通过催化溶液的NMR分析以及推测的催化中间体的模型研究确定。催化反应产生（E）-和（Z）-烯基硅烷，并且氢化硅烷化产物的这两种立体异构体的相对比例明显取决于烯基钌中间体与氢化硅烷的反应过程。因此，有两个反应过程C-H键的形成伴随着通过氧化加成和还原消除的顺序生成甲硅烷基钌中间体。基于机理发现，已经开发了以91-99%的立体选择性独立地产生（E）-和（Z）-烯基硅烷的高效催化剂。新开发的催化剂的催化性能已被证明用于立体控制合成富含（E）和（Z）的聚（2）通过对三氟甲磺酸甲酯配合物的处理，制备了具有独特催化性能的新型钯、铂配合物，它们对共轭二烯的氢胺化反应具有很高的催化活性，（3）合成了一系列硅铂配合物，并通过动力学实验详细研究了它们的C-Si还原消除反应和炔插入反应。与相应的具有铂-碳键的有机铂配合物相比，已发现甲硅烷基铂配合物是高度反应性的

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)。