New Hydrocarbon-Stabilized Metal-Atom Reagents

新型碳氢化合物稳定金属原子试剂

• 批准号: 0841014
• 负责人: John Ellis
• 金额: $ 44.1万
• 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: 2009
• 资助国家: 美国
• 起止时间: 2009-02-01 至 2014-01-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0841014&HistoricalAwards=false
• 关键词: New; Hydrocarbon; Stabilized; Metal; Atom

The Research award in the Inorganic, Bioinorganic and Organometallic Chemistry Program supports the work of Professor John E. Ellis at the University of Minnesota-Twin Cities for research into previously unexplored areas of low valent transition metal chemistry. Objectives include defining the limits of "superreduced" transition metal chemistry and providing new understanding of the reduction of coordinated ligands. Naphthalene, anthracene, and other polycyclic aromatic hydrocarbon,or polyarene, complexes containing transition metals in formal oxidation states that are unprecedented, such as Sc(I-), V(II-), and Cu(I-), or very rare, such as Hf(0, II-), Ta(I, 0), and Ni(I-, II-), will be prepared by reduction of metal halides or related precursors in the presence of these hydrocarbons. The new compounds will be isolated and fully characterized whenever possible. Anionic polyarene-stabilized complexes promise to be of particular interest as unique storable sources of "naked" atomic metal anions, M(Z-). Their reactions with dinitrogen, carbon monoxide, isocyanides, phosphanes, and other acceptor ligands will be explored as a route to hitherto unknown classes of low valent metal complexes. The development of conventional routes to new hydrocarbon-stabilized metal-atom reagents will enable access of such highly-reactive species by other investigators, who do not have access to the specialized and expensive metal-vapor reactor apparatus originally required for the preparation of related species. This project is also important in the education, training, and professional development of a new generation of scientists and educators, including undergraduate and graduate students, visiting faculty, and other post-doctoral associates, where participation by minorities and women is particularly encouraged. Polyarene metal complexes are possible reagents for nitrogen fixation, catalysts for new polymers of unsaturated organic and inorganic species and precursors to novel polymetallics. This project endeavors to develop facile and reproducible routes to new labile hydrocarbon complexes and employ these species as reagents for a general investigation of the chemistry of transition metals in previously unknown or rare formal oxidation states. In this fashion significant contributions to our fundamental understanding of transition metal chemistry are anticipated.

无机、生物无机和有机金属化学项目的研究奖支持明尼苏达大学双城分校的 John E. Ellis 教授对以前未探索的低价过渡金属化学领域的研究。目标包括定义“超还原”过渡金属化学的极限，并提供对配位配体还原的新理解。萘、蒽和其他多环芳烃或聚芳烃，含有前所未有的形式氧化态过渡金属的配合物，如Sc(I-)、V(II-)和Cu(I-)，或非常罕见的，如Hf(0, II-)、Ta(I, 0)和Ni(I-, II-)，可通过金属卤化物或还原剂的还原来制备。 在这些碳氢化合物存在的情况下会产生相关的前体。 只要有可能，新化合物将被分离并充分表征。阴离子聚芳烃稳定的络合物有望作为“裸”原子金属阴离子 M(Z-) 的独特可储存来源而受到特别关注。它们与二氮、一氧化碳、异氰化物、磷烷和其他受体配体的反应将被探索作为迄今为止未知类别的低价金属配合物的途径。开发新的碳氢化合物稳定金属原子试剂的常规途径将使其他研究人员能够获得这种高反应性物质，而他们无法使用最初用于制备相关物质所需的专门且昂贵的金属蒸气反应器设备。该项目对于新一代科学家和教育工作者（包括本科生和研究生、访问教师和其他博士后）的教育、培训和专业发展也很重要，特别鼓励少数族裔和女性的参与。聚芳烃金属配合物可能是固氮试剂、不饱和有机和无机物质新型聚合物的催化剂以及新型多金属化合物的前体。该项目致力于开发新的不稳定烃配合物的简便且可重复的路线，并利用这些物质作为试剂对以前未知或罕见的形式氧化态的过渡金属化学进行一般研究。通过这种方式，预计将对我们对过渡金属化学的基本理解做出重大贡献。