New Horizons in Low-Valent Transition Metal Chemistry

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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.