The Electron-Rich Triple Bond as a Redox Reagent

含有富电子三键的化合物，通常是dihenium，将被用作氧化还原试剂。二膦桥接基团可以通过取代配体内的基团来改变氧化还原电位。将特别强调具有P-H和S-H键的分子，以便评估影响这些配体的非氧化还原活性的因素，以及它们氧化添加到金属-金属键的倾向。这些配合物还将被用作多氢化物的合成前体，并将对这些氢化物的新反应性和结构化学进行研究。在单核铼多氢化物配合物的8位异构体中立体化学刚性的存在将提供一个独特的机会来检查Re-Re与Re-H-Re键在一类迄今为止只发现表现出流动行为的系统中的重要性。在化学学部无机、生物无机和有机金属项目的这个项目中，普渡大学的Richard A. Walton博士将继续研究含有富电子金属-金属键的镝配合物。这些化合物表现出不同寻常的反应性和结构，这项工作的结果将增加我们对有机金属化学的基本知识。这些研究的潜在应用包括某些有毒分子的脱硫和开发更好的加氢过程催化剂。

Compounds that contain the electron-rich triple bond, usually dirhenium species, will be used as redox reagents. A diphosphine bridging group will enable the redox potentials to be varied through substitution of groups within the ligand. Special emphasis will be placed on molecules having P-H and S-H bonds in order to assess the factors that influence the non-redox activity of these ligands versus their tendency to oxidatively add to the metal-metal bond. The complexes will also be used as synthetic precursors to dirhenium polyhydrides, and the novel reactivity and structural chemistry of these hydrides will be examined. The existence of stereochemical rigidity in 8-coordinate isomers of mononuclear rhenium polyhydride complexes will provide a unique opportunity to examine the importance of Re-Re versus Re-H-Re bonding in systems of a type that heretofore have only been found to exhibit fluxional behavior. %%% In this project in the Inorganic, Bioinorganic, and Organometallic Program of the Chemistry Division, Dr. Richard A. Walton of Purdue University will continue studies of dirhenium complexes that contain electron rich metal-metal bonds. These compounds exhibit unusual reactivity and structures, and the results of this work will increase our basic knowledge of organometallic chemistry. Potential applications of these studies include desulfurization of certain toxic molecules and the development of better catalysts for hydrogenation processes.