Chemistry of Low-Coordinate Nickel

低配位镍的化学

• 批准号: 0615274
• 负责人: Gregory Hillhouse
• 金额: --
• 依托单位: University of Chicago
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2006
• 资助国家: 美国
• 起止时间: 2006-08-15 至 2010-01-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0615274&HistoricalAwards=false
• 关键词: Chemistry; Low; Coordinate; Nickel

With the support of the Inorganic, Bioinorganic and Organometallics Chemistry Program, Professor Gregory L. Hillhouse of the Department of Chemistry at the University of Chicago will research the chemistry of three-coordinate nickel complexes with emphasis on nickel-ligand multiple bonds including imido and carbene ligands. His group will focus their efforts first on understanding the interaction of olefins with (dtbpe)Ni=NR complexes (dtbpe = 1,2-bid(di-tert-butylphosphino)ethane) that result in NR-transfer to the olefin and the generation of aziridines. The second part or their research will focus on extending the group-transfer of imido, phosphinidene, and carbene moieties to other (heteroatom) substituted double bonds. Part three will involve the study of cationic Ni(III) imido complexes, [(dtbpe)Ni=NR+], prepared by the oxidation of the Ni(II) derivatives, to understand their bonding, magnetism, and reaction chemistries. Finally, the synthetic approaches to new multiply-bonded ligands for nickel, focusing on "carbyne" and "nitride" complexs will be examined, with the goal of isolating or trapping these highly-reactive species. This research provides a solid, fundamental understanding of the chemistry of group transfer reactions involving nickel. The studies will have impact in applied ares of inorganic chemistry and catalysis specifically relating to polymerization reactions such as olefin polymerization as well as to areas of organic synthesis related to metal-catalyzed cyclopropanations and aziridinations. This research will also provide insight into the chemistry of Ni(I) and Ni(III), rare oxidation states of emerging importance in the biological chemistry of nickel, especially in nickel-containing enzymes. In addition to the scientific contributions, this project will contribute to human resource develoment and the trianing of the next generation of scientists and teachers. Graduate, undergraduates and high school student will be integral parts of the research team. Participation of underrepresented groups, which in the past have included Hispanic, African-American, sight-disabled and women coworkers, will be actively encouraged.

在无机、生物无机和有机金属化学项目的支持下，芝加哥大学化学系的Gregory L. Hillhouse教授将研究三配位镍配合物的化学，重点是包括亚氨基和卡宾在内的镍配体多重键配体。 他的团队将首先集中精力了解烯烃与 (dtbpe)Ni=NR 配合物（dtbpe = 1,2-双（二叔丁基膦）乙烷）的相互作用，从而导致 NR 转移到烯烃并生成氮丙啶。 第二部分或他们的研究将集中于将亚氨基、次膦亚基和卡宾部分的基团转移扩展到其他（杂原子）取代的双键。 第三部分将研究通过氧化 Ni(II) 衍生物制备的阳离子 Ni(III) 亚氨基配合物 [(dtbpe)Ni=NR+]，以了解它们的键合、磁性和反应化学性质。 最后，将研究新型镍多键配体的合成方法，重点关注“碳炔”和“氮化物”配合物，目的是分离或捕获这些高反应性物质。 这项研究为涉及镍的基团转移反应的化学提供了坚实的基础理解。 这些研究将对无机化学和催化应用领域产生影响，特别是与聚合反应（例如烯烃聚合）以及与金属催化环丙烷化和氮丙啶化相关的有机合成领域。 这项研究还将深入了解 Ni(I) 和 Ni(III) 的化学性质，这两种稀有氧化态在镍的生物化学中，特别是在含镍酶中具有新兴的重要性。 除了科学贡献外，该项目还将有助于人力资源开发以及下一代科学家和教师的培养。 研究生、本科生和高中生将成为研究团队的组成部分。 将积极鼓励代表性不足的群体（过去包括西班牙裔、非裔美国人、视力障碍者和女性同事）的参与。