Dioxygen Activation with Nickel Complexes

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This award in the Inorganic, Bioinorganic and Organometallic Chemistry program supports research by Professor Charles G. Riordan at the University of Delaware to develop the coordination chemistry of nickel in its monovalent oxidation state to activate dioxygen and related small molecules. The approach combines coordination chemistry with spectroscopic techniques, augmented with computational studies, to generate a detailed understanding of geometric and electronic structures of novel reactive intermediates. Long-term objectives include advancing these new species in stoichiometric and catalytic oxidations of organic molecules. Complementary studies aim to activate elemental sulfur and selenium to produce new, soluble Ni-S and Ni-Se structures Related studies of the heavier O2 congeners, S8 and Se, complement these studies affording the opportunity to gain comparative insight into small molecule/element reductive activation. This program aims to advance the fundamental understanding of nickel-based dioxygen activation through systematic studies designed to address issues of structure, mechanism of formation and inherent reactivity characteristics. Undergraduate, graduate and postdoctoral students will develop a range of technical skills in areas including chemical synthesis, anaerobic and cryogenic methodologies, advanced spectroscopic methods and kinetics while developing intellectual breadth in the underlying principles of contemporary inorganic chemistry. Interactions with laboratories at Wisconsin-Madison and California-Davis will expose students to collaborative approaches in problem solving.