Metal-oxo and Metal-peroxo Complexes in Oxidative Catalysis

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Most chemicals derive from a just a few simple starting materials yet chemical synthesis has a major impact on the economy of the United States, contributing more than 30% of the Gross National Product (GNP). In this project, with the support from the Chemical Catalysis (CAT) Program in the Division of Chemistry, Professor John Groves of Princeton University seeks to design new chemical processes to make high value chemicals. The new synthetic methods may be used to make new drugs and agrichemicals. The research combines laboratory experiments and computer calculations to predict and verify how the reactions progress. The ultimate goal of this work is to replace expensive metal catalysts with less inexpensive metals that are more effective in convert carbon-hydrogen (C-H) bonds to carbon-fluorine (C-F) bonds. This research illustrates the detailed pathways for the new chemical reactions. The research group of Professor Groves trains future scientists, especially women and those that are under-represented in science. These scientists gain both technical training and mentoring so that they are successful in careers in teaching, research, and industry.More than 95% of industrially-produced chemicals are derived from a small slate of simple, molecular building blocks. Chemical manufacturing contributes more than 30% of the GNP of the United States. With funding from the Chemical Catalysis Program of the Chemistry Division, Professor Groves of Princeton University is developing new methods for the catalytic oxygenation, fluorination and pseudo-halogenation of C-H bonds. Such processes are of fundamental interest as they inpact the economic value of the pharmaceutical, agrochemical and chemical process industries. The development of such novel oxidative processes requires a thorough understanding of the mechanisms of metal-mediated atom transfer. The project aims to observe the unitary processes of catalysis by characterizing reactive metal oxo and metal peroxo intermediates and elucidating the nature of their reactions with organic substrates. In particular, the research elaborates a conceptual basis for heteroatom rebound catalysis (HRC), which can be dissected in a manner similar to hydrogen atom transfer. The project integrates small molecule chemical catalysts with insights from metalloenzymes and biocatalytic processes. Through analogies with Nature, the redox chemistry of iron, manganese, cobalt and other metals can add significantly to understanding and increased capabilities in chemical catalysis. The Groves group at Princeton University trains students and postdoctoral research associates, especially under-represented minorities and women, through the NSF Research Experiences for Undergraduates Programs, the Girls Science, Technology, Engineering and Mathematics Summer Program (GSTEM), and Princeton Chemistry's summer diversity program.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.