The Electron-Rich Triple Bond as a Redox Reagent

作为氧化还原试剂的富电子三键

• 批准号: 9107578
• 负责人: Richard Walton
• 金额: $ 34.07万
• 依托单位: Purdue Research Foundation
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1991
• 资助国家: 美国
• 起止时间: 1991-06-15 至 1994-11-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9107578&HistoricalAwards=false
• 关键词: Electron; Rich; Triple; Bond; Redox

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.

含有富电子三键的化合物，通常 二铼物质将用作氧化还原试剂。 一 二膦桥连基团将使氧化还原电位 可以通过取代配体内的基团而变化。 将特别强调具有P-H和S-H的分子 债券，以评估影响因素， 这些配体的非氧化还原活性与它们的倾向， 氧化性地添加到金属-金属键。 该复合体将 也可用作聚二铼的合成前体， 以及这些化合物的新型反应性和结构化学， 他将接受检查。 立体化学的存在 单核双金属8配位异构体的刚性 聚氢化物复合物将提供一个独特的机会， 研究Re-Re与Re-H-Re键合在 迄今为止只发现的一种类型的系统 表现出流动性。 %%% 在这个项目中，无机，生物无机， 化学部的有机程序，理查德博士 A.普渡大学的沃尔顿将继续研究 含有富电子金属-金属的二铼络合物 债券 这些化合物表现出不寻常的反应性， 结构，这项工作的结果将增加我们的 有机金属化学的基本知识。 潜在 这些研究的应用包括 某些有毒分子和开发更好的催化剂 用于氢化过程。