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

该项目由无机化学、生物无机化学和金属有机化学计划资助，将支持密苏里大学圣路易斯分校的戈登·安德森教授对铂和/或钯两种类型的双金属络合物的研究。第一类是由(二芳基膦)环戊二烯配体桥联的同核双铂烷基配合物。这些络合物将被用作研究双核单元内的羰化反应和烷烃消除反应机理的平台。要研究的第二类双核配合物是氢化物桥联的同核和异核钯、铂配合物，其双核结构是基于桥联双(二苯基膦)甲烷及其相关配体的。异核配合物的烷基衍生物将用于研究(烷烃)的竞争还原消除和竞争亲电的M-C键断裂反应。同核双钯配合物为研究通常高度不稳定的氢化钯络合物的化学性质提供了一个独特的机会。核磁共振波谱将被广泛用于研究这些反应。催化对于提高许多工业过程的速度和选择性是必要的。合理设计新的、甚至改进的催化系统需要详细了解参与催化循环的各个步骤。这项工作的目的是加深对金属络合物反应的基本了解，这些反应经常涉及到催化。这些研究的结果最终可能被用于开发具有工业意义的新的催化工艺。

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.