Chemistry of Three-Coordinate Nickel Complexes containing Nickel-Ligand Multiple Bonds

芝加哥大学化学系Gregory L.Hillhouse博士由化学部无机化学、生物无机化学和金属有机化学项目支持，致力于研究含镍配体多键的三配位镍配合物的化学。该项目包括三个部分。第一部分将集中研究镍的亚胺、亚膦和卡宾络合物的成键和反应活性。这项工作的目的是定义镍配体多键的基本性质。第二部分涉及Ni(I)，重点介绍了具有一系列辅助配体的衍生物的制备，用于反应性研究和光谱表征，这将被证明对检测和表征Ni(I)中间体是有用的。阐明镍(I)-烷基配合物的有机金属化学也将是一个焦点。这些研究还将有助于更好地确定Ni(I)/Ni(II)氧化还原对，并评估其对反应活性的影响。第三部分涉及对不寻常的三配位Ni(II)配位阳离子的研究，这些阳离子被证明具有特殊的反应活性。这项研究将提供对镍(I)化学的坚实理解，镍(I)是一种罕见的氧化态，但在镍的生物化学中，尤其是在含镍的酶中，镍(I)的重要性正在显现。此外，这些研究将在应用无机化学和催化方面产生影响，特别是在与镍(II)阳离子影响的聚合反应相关的领域，如烯烃聚合和CO/烯烃共聚，以及有机合成，如金属催化的环丙化和氮杂环化。除了科学贡献外，该项目还将有助于人力资源开发和下一代科学家和教师的培训。本科生和高中生都将是研究团队不可或缺的一部分。将积极鼓励代表性不足的少数群体的参与，其中包括西班牙裔、非裔美国人和女性同事。

Dr. Gregory L. Hillhouse, Chemistry Department, University of Chicago, is supported by the Inorganic, Bioinorganic, and Organometallic Chemistry Program of the Chemistry Division for research into the chemistry of three-coordinate nickel complexes containing nickel-ligand multiple bonds. There are three parts of the project. The first will concentrate on studies of the bonding and reactivity of imido, phosphinidene, and carbene complexes of Ni. This work will be aimed at defining the fundamental nature of Ni-ligand multiple bonds. The second part involves Ni(I) and emphasizes the preparation of derivatives with a range of ancillary ligands for reactivity studies and spectroscopic characterization, which will prove useful in detecting and characterizing Ni(I) intermediates. Elucidation of the organometallic chemistry of Ni(I)-alkyl complexes will also be a focus. These studies also will help to better define the Ni(I)/Ni(II) redox couple and assess its implications for reactivity. The third part involves studies of the unusual, 3-coordinate Ni(II) complex cations, which are proving to possess exceptional reactivity. This research will provide a solid understanding of the chemistry of nickel(I), a rare oxidation state, but one of emerging importance in the biological chemistry of nickel, especially in nickel-containing enzymes. Additionally, these studies will have impact in applied inorganic chemistry and catalysis, specifically in areas relating to polymerization reactions effected by nickel(II) cations, such as olefin polymerization and CO/olefin copolymerizations, and organic synthesis, such as metal-catalyzed cyclopropanations and aziridinations. In addition to the scientific contributions, this project will contribute to human resource development and the training of the next generation of scientists and teachers. Both undergraduates and high school students will be integral parts of the research team. Participation of underrepresented minorities, which in the past have included Hispanic, African- American, and women coworkers, will be actively encouraged.