Transition Metal Silicon Chemistry and Development of Novel Pi Systems

T.Don Tilley博士，加州大学伯克利分校化学系，由化学部无机化学、生物无机化学和金属有机化学项目支持，用于研究连接的活性硅中间体的金属络合物。为了操纵金属-硅双键的性质，将制备一系列新的硅烯络合物，在硅上连接各种sigma和pi供体基团。将检查这些化合物的稳定性和化学反应活性，以确定发生在硅-碳多键上的反应的化学性质和机理。将特别强调-硅基和-硅烯的迁移以及络合物的催化性能的发展。金属配位将被用来稳定含有重14族元素的pi-体系。整个化学领域--有机金属化学--关注的是具有金属-碳键的化合物的行为。这是一个对催化和化学合成极其重要的领域，无论是在实验室还是在工业环境中都是如此。在元素周期表中，硅位于碳的下方。因此，这两种元素的化学成分既有相似之处，也有不同之处，金属-硅相互作用的性质具有内在重要性。在这个项目中，我们将制备各种含有金属-硅多键的化合物，并使它们的化学系统化。这将为催化剂、试剂、化学转化和使用金属-硅化合物的新材料的开发提供背景。

Dr. T. Don Tilley, Chemistry Department, University of California - Berkeley, is supported by the Inorganic, Bioinorganic, and Organometallic Chemistry Program of the Chemistry Division for the study of metal complexes with ligated reactive silicon intermediates. In order to manipulate the nature of the metal-silicon double bond, a series on new silylene complexes will be prepared with a variety of sigma and pi donating groups attached to silicon. The stability and chemical reactivity of these compounds will be examined to establish the chemical properties and mechanisms of reactions that occur at the silicon-carbon multiple bond. Special emphasis will be paid to -silyl and -silylene migrations and to the development of catalytic properties of the complexes. Metal coordination will be utilized to stabilize pi-systems containing heavy group 14 elements. An entire field of chemistry - organometallic chemistry - is concerned with the behavior of compounds with metal-carbon bonds. This is an area of tremendous importance to catalysis and chemical synthesis, as practiced both in laboratory and industrial settings. Silicon lies just below carbon in the periodic chart. Thus, there are both similarities and differences in the chemistries of the two elements and the nature of the metal-silicon interaction is of intrinsic importance. In this project a variety of compounds containing metal-silicon multiple bonds will be prepared and their chemistry systematized. This will provide the background for the development of catalysts, reagents, chemical transformations, and new materials using metal-silicon compounds.