This award in the Chemical Synthesis (SYN) program supports work by Professor Charles G. Riordan at the University of Delaware to carry out fundamental studies on the reaction of nickel complexes with dioxygen. Using ligand design and chemical synthesis strategies, new nickel-superoxo, -alkylperoxo and -hydroperoxo complexes are sought. The geometric and electronic structures will be defined by applying a range of spectroscopic methods. Reactivity of the new molecules with exogenous substrates susceptible to oxygen atom transfer and C-H activation will be explored in an effort to correlate structure with reactivity. Complementary efforts are aimed at garnering evidence for high-valent oxonickel intermediates. These studies require that student coworkers develop intellectual breadth in synthetic and mechanistic inorganic chemistry and molecular alternative energy. They further afford students the opportunity to collaborate on advanced spectroscopic measurements with colleagues at the Universities of Wisconsin-Madison and California-Davis.
Metal-mediated oxygen activation is a central process in Nature as well as the chemical and pharmaceutical industries. The development of new reagents using abundant, i.e. cheap metals, for stoichiometric and catalytic oxidation of organic molecules remains a significant challenge. The fundamental studies of this project will provide insight into how to harness the redox attributes of nickel for these chemical transformations.
