New Horizons in Low-Valent Transition Metal Chemistry

低价过渡金属化学的新视野

• 批准号: 0348349
• 负责人: John Ellis
• 金额: --
• 依托单位: University of Minnesota-Twin Cities
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2004
• 资助国家: 美国
• 起止时间: 2004-04-01 至 2009-03-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0348349&HistoricalAwards=false
• 关键词: New; Horizons; Low; Valent; Transition

The Inorganic, Bioinorganic, and Organometallic Chemistry Program of the Chemistry Division supports Dr. John Ellis, Department of Chemistry, University of Minnesota, for research into low valent transition metal chemistry. The overall objective of the project is to obtain transition metal species containing metals in rare or previously unknown low formal oxidation states. The study will seek to define the boundaries of "superreduced" transition metal chemistry and provide insights on the relative susceptibility of coordinated ligands towards reduction. Polyarene complexes of transition metals in formal oxidation states that are unprecedented, such as Ni(I-), Pt(I-), and Cu(I-), or very rare, such as Hf(0, II-), and Ta(0) will be prepared by reduction of metal halides in the presence of arenes. The ability of species such as isocyanides, phosphanes, phosphites, and cyclooctatetraene to displace the arene ligands will be explored as a route to heretofore unknown types of low valent metal complexes. Polyarene metal complexes are possible reagents for nitrogen fixation, catalysts for the polymerization of a variety of unsaturated organic species and precursors to novel polymetallics. This project will develop simple preparations for polyarene complexes and extend the chemistry to metals where low valent complexes are either unknown or very unusual. Thus, it will form the foundation from which applications, such as catalysis, can be devised. A most important broader impact will be in the education, training and professional development of undergraduate and graduate students and postdoctoral associates.

化学部的无机，生物无机和有机化学计划支持明尼苏达大学化学系的John Ellis博士研究低价过渡金属化学。该项目的总体目标是获得含有稀有或以前未知的低形式氧化态金属的过渡金属物种。该研究将寻求定义“超还原”过渡金属化学的边界，并提供有关配位配体对还原的相对敏感性的见解。 在芳烃存在下，通过还原金属卤化物，将制备处于形式氧化态的过渡金属的聚芳烃络合物，所述形式氧化态是前所未有的，如Ni（I-）、Pt（I-）和Cu（I-），或非常罕见的，如Hf（0，II-）和Ta（0）。将探索诸如异氰化物、膦、亚磷酸酯和环辛四烯等物质置换芳烃配体的能力，作为迄今未知类型的低价金属络合物的途径。聚芳烃金属配合物是可能的固氮试剂、各种不饱和有机物聚合的催化剂和新型多金属化合物的前体。这个项目将开发聚芳烃络合物的简单制备，并将化学扩展到金属，其中低价络合物是未知的或非常罕见的。因此，它将成为设计应用（如催化）的基础。一个最重要的更广泛的影响将是在教育，培训和专业发展的本科生和研究生和博士后助理。