Synthesis and Study of Cationic Gold pi-Complexes

阳离子金π配合物的合成与研究

• 批准号: 0911265
• 负责人: Ross Widenhoefer
• 金额: $ 43.5万
• 依托单位: Duke University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2009
• 资助国家: 美国
• 起止时间: 2009-08-15 至 2012-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0911265&HistoricalAwards=false
• 关键词: Synthesis; Study; Cationic; Gold; pi

This project is directed toward the syntheses and study of cationic, 14-electron gold(I) pi-alkene, pi-allene, and pi-alkyne complexes. Cationic gold(I) complexes have recently emerged as effective catalysts for the functionalization of C-C multiple bonds with carbon and heteroatom nucleophiles. However, the cationic, two-coordinate gold(I) pi-complexes germane to catalysis remain scarce and, as a result, little is known about the structure and reactivity of these important complexes. Execution of the proposed research activities will fill this gap in our understanding. Studies directed toward realizing this objective include analysis of 1) the ground-state structure and fluxional behavior of cationic gold(I) pi-complexes, 2) the relative binding ability pi-hydrocarbyl ligands to a cationic gold fragment, 3) the kinetics of degenerative ligand exchange of cationic gold(I) pi-complexes, and 4) the reactivity of gold pi-complexes toward nucleophiles. With this award, the Organic and Macromolecular Chemistry Program is supporting the research of Professor Ross Widenhoefer of the Department of Chemistry at Duke University. Professor Widenhoefer's research efforts are directed, in large part, to the mechanistic analysis of the gold(I)-catalyzed addition of carbon and heteroatom nucleophiles to alkenes and allenes. Realization of the proposed activities will provide mechanistic information valuable to the ever-growing global community of researchers working toward the development of new and more efficient gold(I) catalyzed transformations for application in organic synthesis and pharmaceutical development.

该项目旨在合成和研究阳离子、14 电子金 (I) π-烯烃、π-丙二烯和 π-炔络合物。 阳离子金 (I) 配合物最近已成为碳和杂原子亲核试剂对 C-C 多重键进行官能化的有效催化剂。 然而，与催化作用密切相关的阳离子二配位金（I）π配合物仍然很少，因此，人们对这些重要配合物的结构和反应性知之甚少。 执行拟议的研究活动将填补我们理解上的这一空白。 旨在实现这一目标的研究包括分析 1) 阳离子金 (I) π-配合物的基态结构和通量行为，2) π-烃基配体与阳离子金片段的相对结合能力，3) 动力学阳离子金(I) pi 络合物的简并配体交换，以及4) 金pi 络合物对亲核试剂的反应性。 有机与高分子化学项目通过该奖项支持杜克大学化学系 Ross Widenhoefer 教授的研究。 Widenhoefer 教授的研究工作在很大程度上针对金 (I) 催化碳和杂原子亲核试剂与烯烃和丙二烯的加成反应的机理分析。 拟议活动的实现将为不断增长的全球研究人员群体提供有价值的机械信息，这些研究人员致力于开发新的、更有效的金 (I) 催化转化，以应用于有机合成和药物开发。