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

在这个无机、生物无机和有机金属项目中，加州大学圣地亚哥分校的T. Don Tilley博士将制备含有活性硅的过渡金属配合物。已知过渡金属配合物可作为硅化合物反应的催化剂，并可作为制备含硅聚合物的催化剂。这些聚合物具有结构和电子特性，可用于各种应用。通过类比对碳烯（在碳氢化合物的聚合物形成中很重要）的研究，Tilley将制备配合物，以帮助阐明过渡金属配位球中含硅碎片的化学性质。硅烯、硅烯和二烯配合物可作为合成单体和聚合物硅化合物的中间体。例如，硅烯配合物可以是聚硅烷聚合物中金属催化的Si-Si键形成的中间体。过渡金属对硅的活化模式将通过获取有关eta-2-硅烷配合物的形成、硅基向金属中心的迁移以及脱氢硅烷偶联的机制信息来研究。其中使用的金属将是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.