Metal-Oxo and Metal-Peroxo Intermediates in Oxidative Catalysis

Princeton University, Princeton NJ

Investigators

Abstract

In this project funded by the Chemical Catalysis program of the Chemistry Division, Professor John Groves of Princeton University is developing catalysts that can form carbon-fluorine bonds in hydrocarbons. Researchers on this project are also studying the reaction mechanisms and the factors that control the chemistry of the catalytic reactions, which will help to optimize the outcomes of the catalysis and to add to our fundamental knowledge base about chemistry. Hydrocarbon transformations play central roles in the chemical process industry and the global energy budget. Compounds that contain carbon-fluorine bonds are important for a range of technologies, including those involving PET (Positron Emission Tomography) scans, and the production of pharmaceuticals, agrochemicals, and coatings. So the chemistry for advanced technological opportunities in the 21st century and to train the teachers of science for the future. Professor Groves is developing new methods for the catalytic oxygenation, fluorination and pseudo-halogenation of aliphatic carbon-hydrogen bonds. Such processes continue to be of fundamental interest and of greatly increasing economic value. The development of such novel oxidative processes requires a thorough understanding of the mechanisms of metal-mediated oxygen, and halogen, activation and transfer. One ongoing aspect of the project involves characterizing reactive metal oxo and metal peroxo intermediates and elucidating the nature of their reactions with organic substrates. This research is addressing five inter-related areas: (1) New methods and mechanisms of fluorination of unactivated C-H bonds, (2) New catalytic methods for pseudo-halide transfer to C-H bonds for carbon-nitrogen bond formation, (3) Using protons to tune catalytic C-H bond oxygenation in the regime of entropy control, (4) Energy landscapes for electrocatalytic oxygen transfer to and from oxygen and halogens, (5) C-H oxygenations by high-valent iodyl and iodosyl cations for natural gas partial oxidation.