Chemistry of Low-Coordinate Nickel

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格雷戈里·L·希尔豪斯教授将研究三配位镍配合物的化学，重点是镍-配体多键，包括亚胺和卡宾配体。他的团队将首先致力于了解(Dtbpe)Ni=NR络合物(dtbpe=1，2-BID(二叔丁基膦)乙烷)与烯烃的相互作用，从而导致NR-转移到烯烃并生成氮杂环丙烷。第二部分或他们的研究将集中在将亚胺、亚膦和卡宾部分的基团转移到其他(杂原子)取代的双键上。第三部分研究了由Ni(II)衍生物氧化得到的阳离子Ni(III)亚胺配合物[(Dtbpe)Ni=NR+]，以了解它们的成键、磁性和反应化学性质。最后，我们将考察新的镍多键配体的合成方法，重点是“卡宾”和“氮化物”络合物，目的是分离或捕获这些高活性物种。这项研究提供了对涉及镍的基团转移反应的化学的坚实的、基本的理解。这些研究将对无机化学和催化的应用领域产生影响，特别是与聚合反应有关的聚合反应，如烯烃聚合，以及与金属催化的环丙化和氮杂环化有关的有机合成领域。这项研究还将深入了解镍(I)和镍(III)的化学，这是镍的生物化学中新出现的重要的稀有氧化态，特别是在含镍的酶中。除了科学贡献外，该项目还将为人力资源开发和下一代科学家和教师的试验做出贡献。研究生、本科生和高中生将是研究团队不可或缺的一部分。将积极鼓励代表人数不足的群体参加，其中包括西班牙裔、非裔美国人、视障人士和女性同事。

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.