Redox Reactivity of Rhenium Polyhydrides and Triple Bonds

9409932 Walton普渡大学化学系Richard A. Walton博士，受化学系无机、生物无机和有机金属化学项目的支持，对铼多氢化物和含铼-铼三键化合物的氧化还原反应性进行了研究。研究了Re-Re三键诱导的还原偶联反应机理和含3-金属呋喃环配合物的反应性。七氢化铼与各种有机酸的反应将作为生成立体化学刚性8配位分子的途径。在某些氢化物体系中发生的不寻常的内炔到端炔异构化将被用来制备铼-烷基炔配合物。这个项目的一部分旨在开发含有两个直接键合铼原子的化合物为一氧化碳等小分子提供电子的能力。这些电子的加入将使小分子相互结合，或与附近的其他分子结合，从而形成更扩展的结构。这种行为在工业和实验室过程中都很重要。在第二部分的研究中，将制备被8个其他基团包围的铼化合物。这些非常拥挤的分子有望在与它们相互作用的分子中引起许多新的反应。

9409932 Walton Purdue Univ. Dr. Richard A. Walton, Chemistry Department, Purdue University, is supported by the Inorganic, Bioinorganic, and Organometallic Chemistry Program of the Chemistry Division for an investigation of the redox reactivity of rhenium polyhydrides and compounds containing rhenium-rhenium triple bonds. The mechanism of reductive coupling reactions induced by the Re-Re triple bond and the reactivity of complexes containing the 3-metallafuran ring will be examined. The reactions of rhenium-heptahydrides with various organic acids will be explored as routes to stereochemically rigid 8-coordinate molecules. The unusual isomerization of internal to terminal alkynes which occurs in some of the hydride systems will be utilized to prepare rhenium-alkylidyne complexes. A portion of this project is aimed at developing the ability of compounds which contain two directly bonded rhenium atoms to supply electrons to small molecules such as carbon monoxide. The addition of these electrons will cause the small molecules to bond to one another, or to other nearby molecules, thereby forming more exended structures. Such behavior is important in both industrial and laboratory processes. In the second part of the research, rhenium compounds surrounded by 8 other groups will be prepared. These very crowded molecules are expected to be capable of inducing a number of new reactions in molecules with which they interact.