Synthesis and Study of Transition-Metal Complexes of Reactive Silicon Intermediates

在这个项目中，加州大学圣地亚哥分校的T.Don Tilley博士将制备含有活性硅物种的过渡金属配合物。已知过渡金属络合物可用作硅化合物反应的催化剂，也可用作制备含硅聚合物的催化剂。这些聚合物可能具有在不同应用中有用的结构和电子性质。通过类似于对卡宾(在碳氢化合物的聚合物形成中很重要)的研究，Tilley将制备络合物，以帮助了解过渡金属配位球中含硅碎片的化学性质。将制备硅烯、硅烯和二硅烯的络合物，它们可以作为合成单体和聚合硅化合物的新方法的中间体。例如，在聚硅烷聚合物中，硅烯络合物可能是金属催化的硅-硅键形成的中间体。通过获得ETA-2-硅烷络合物的形成、硅基向金属中心的迁移以及脱氢硅烷偶联等机理信息，研究过渡金属对硅的活化方式。使用的金属包括Ru、Pt、Rh、Ir、W、Os和Mo。

In this project in the Inorganic, Bioinorganic, and Organometallic Program, Dr. T. Don Tilley of the University of California at San Diego will prepare transition metal complexes containing reactive silicon species. Transition metal complexes are known to act as catalysts for reactions of silicon compounds and may serve as catalysts for the preparation of silicon-containing polymers. These polymers could have structural and electronic properties useful in diverse applications. By analogy to studies of carbenes (important in polymer formation in hydrocarbons), Tilley will prepare complexes to help eludicate the chemical properties of silicon-containing fragments in the coordination sphere of transition metals. Complexes of silylenes, silenes, and disilenes which could serve as intermediates in new synthetic methods for monomeric and polymeric silicon compounds will be prepared. For example, silylene complexes may be intermediates in metal-catalyzed Si-Si bond formation in polysilane polymers. Modes of silicon activation by transition metals will be studied by acquiring mechanistic information on formation of eta-2-silane complexes, migration of silyl groups to a metal center, and dehyrogenative silane coupling. Among the metals used will be Ru, Pt, Rh, Ir, W, Os, and Mo.