Redox Reactivity of Rhenium Polyhydrides and Triple Bonds

9409932沃尔顿普渡大学。普渡大学化学系Richard A.Walton博士受化学部无机化学、生物无机化学和金属有机化学项目的支持，致力于研究Re多氢化物和含Re-Re三键化合物的氧化还原反应性。研究了Re-Re三键引发还原偶联反应的机理以及含3-金属呋喃环的配合物的反应活性。作为立体化学刚性的8配位分子的途径，七氢锗与各种有机酸的反应将被探索。在一些氢化物体系中发生的从内部到末端的异构化反应将被用来制备Re-亚烷基络合物。该项目的一部分旨在发展含有两个直接键合的Re原子的化合物向一氧化碳等小分子提供电子的能力。这些电子的加入将导致小分子相互结合，或与附近的其他分子结合，从而形成更多的伸展结构。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，将制备被其他8个基团包围的Re化合物。这些非常拥挤的分子有望能够在它们相互作用的分子中引发一些新的反应。

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.