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，生物有机和有机金属化学计划的支持下，芝加哥大学化学系的Gregory L. Hillhouse教授将研究三层坐标镍络合物的化学，重点介绍了包括Imido和Carbene Ligands在内的镍配体多种债券。 他的小组将首先将精力集中在理解烯烃与（DTBPE）Ni = NR复合物（DTBPE = 1,2-bid（Di-TERT叔丁基磷酸）乙烷）中的相互作用，从而导致NR-TRANSFER向烯烃转移到烯烃和Aziridines的产生。 第二部分或他们的研究将集中于将imido，phosphinidene和Carbene部分的群体转移扩展到其他（杂原子）取代的双键。 第三部分将涉及阳离子Ni（III）Imido复合物，[（DTBPE）Ni = nr+]，通过Ni（ii）衍生物的氧化制备，以了解其键合，磁性和反应化学。 最后，将检查针对镍新的多键配体的合成方法，重点关注“ Carbyne”和“ Nitride”络合物，目的是隔离或捕获这些高反应性的物种。 这项研究为涉及镍的群体转移反应的化学反应提供了坚实的，基本的理解。 这项研究将影响与聚合反应（例如烯烃聚合）以及与金属催化环环和氮杂酶相关的有机合成区域的非有机化学ARE和催化。 这项研究还将洞悉Ni（I）和Ni（III）的化学，这是罕见的氧化态在镍的生物学中，特别是在含镍酶中的生物化学重要性。 除了科学贡献外，该项目还将有助于人力资源和下一代科学家和教师的三角。 研究生，本科生和高中生将成为研究团队不可或缺的一部分。 将会积极鼓励代表性不足的团体的参与，包括西班牙裔，非洲裔美国人，观光者和女同事。