CAS: Metal-oxo and Metal-peroxo Complexes in Oxidative Catalysis

With the funding from the Chemical Catalysis Program of the Division of Chemistry, Professor John T. Groves of Princeton University and his research group will develop and study catalysts to enable energy-efficient chemical transformations such as C-H activation to better access high added-value chemical products. More than 95% of chemical industry products derive from a small slate of molecular building blocks that are relevant to more than 30% of the GNP of the United States. It is the central thesis of this project that recent conceptual advances in oxidative chemical and biochemical catalysis, and the interplay of emerging experimental techniques and modern theory, offer unprecedented opportunities to develop inexpensive, earth-abundant transition metals as catalysts for these selective processes. The project combines knowledge of biocatalysis used by microorganisms with insights derived from synthetic systems to provide a conceptual basis to understand these processes. Broad application of this chemistry will have high impact on the nation’s and the world’s chemical and energy economies. The Groves group will continue to serve as an effective training ground for graduate students and postdoctoral research associates, especially women and members of under-represented groups in science. In this project, Professor Groves aims to develop new methods for the catalytic oxygenation, fluorination and halogenation of C-H bonds. The development of novel and efficient oxidative processes requires a thorough understanding of the mechanisms of metal-mediated atom transfer by observing the unitary processes of catalysis, also including a range of metal-halogen species, and elucidating the nature of their reactions with organic substrates. In particular, the proposed research strives to elaborate a conceptual basis for heteroatom rebound catalysis, which can be dissected in a manner similar to hydrogen atom transfer. The project will integrate small molecule chemical catalysts with insights from metalloenzymes and biocatalytic processes. Nature employs iron proteins to achieve C-H hydroxylations and halogenations. Through analogy, the redox chemistry of Fe, Mn, Co and other abundant transition metals will add significantly to our fundamental understanding of reactive metal species, of the utility of new kinetic probes, and likely afford a deeper understanding of electronic structure and of the power of computation. In the end, this work is expected to offer opportunities to realize a detailed quantitative and predictive understanding of oxidative catalysis. This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.