Chemistry of Platinum and Palladium Complexes Bridged by Phosphinocyclopentadienyl or Diphosphine Ligands

该项目由无机，生物无机和有机生物学资助， 化学计划，将支持戈登安德森教授的研究， 位于圣路易斯的密苏里州大学， 铂和/或钯的络合物。 第一种类型是homemorphism 由以下基团桥连的双铂烷基络合物： （二芳基膦基）膦配体。 这些复合物将用于 作为研究羰基化机理的平台， 双核单元内的烷烃消除反应。 第二类型 的双核配合物进行了研究是氢化物桥连的homo-和 双核结构的钯和铂的杂合配合物， 基于桥连双（二苯基膦基）甲烷和相关的 配体。 将使用杂环配合物的烷基衍生物 研究烷烃的竞争还原消除， 亲电M-C键断裂反应。 二钯合钯 复合物提供了一个独特的机会，研究化学性质， 钯氢化物络合物，这通常是非常不稳定的。 NMR 光谱学将被广泛用于研究这些反应。 催化对于提高反应速率和通常的选择性是必要的。 许多工业过程。新的，甚至是改进的， 催化系统需要详细了解各个步骤 参与到催化循环中。 这项工作旨在 发展对某些络合物反应的基本认识 催化作用中经常涉及的金属。 的结果 这些研究最终可能用于开发新的催化方法 工业重要性。

This project, funded by the Inorganic, Bioinorganic and Organometallic Chemistry Program, will support studies by Professor Gordon Anderson of the University of Missouri, St. Louis, on two types of bimetallic complexes of platinum and/or palladium. The first type are homonuclear diplatinum alkyl complexes that are bridged by (diarylphosphino)cyclopentadienyl ligands. These complexes will be used as a platform for the investigation of mechanisms of carbonylation and alkane elimination reactions within the dinuclear unit. The second type of dinuclear complexes to be investigated are hydride bridged homo- and heteronuclear palladium and platinum complexes whose dinuclear structures are based upon bridging bis(diphenylphosphino)methane and related ligands. Alkyl derivatives of the heteronuclear complexes will be used to study competitive reductive elimination (of alkane), and competitive electrophilic M-C bond cleavage reaction. The homonuclear dipalladium complexes provide a unique opportunity to study the chemical properties of palladium hydride complexes, which are normally highly unstable. NMR spectroscopy will be used extensively for investigating these reactions. Catalysis is necessary to increase the rates and often the selectivity of many industrial processes. The rational design of new, or even improved, catalytic systems requires detailed knowledge of the individual steps that participate in the catalytic cycle. This work is aimed at developing the fundamental understanding of some reactions of complexes of metals that are frequently involved in catalysis. The results of these studies may ultimately be used to develop new catalytic processes of industrial importance.