Understanding and Directing the Reactivity of Cyclometalated Complexes in Late Transition Metal-Based Homogeneous Catalysis

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With funding from the Chemical Catalysis Program of the Division of Chemistry, Dr. Pinjing Zhao of North Dakota State University Fargo is studying metal-based catalysts for the synthesis of organic molecules. Metal catalysts, molecules that speed up reactions, must interact with the target starting materials (substrates) in order to transform the reactants into products. Dr. Zhao is studying the rational design and development of new catalysts, including those that do not employ expensive and rare metals, to provide new tools for environmentally-friendly chemical synthesis. This project provides interdisciplinary research training and career preparation for graduate and undergraduate students. Catalytic and synthetic reactions are introduced in the sophomore organic chemistry lecture course. Student projects are developed for the inorganic laboratory course to provide hands-on experience with instrumentation and lab techniques. Professor Zhao leads the construction of a web-based database to promote general dissemination of the fundamental knowledge and recent research progress on organometallic chemistry. This database provides valuable training experiences for graduate and undergraduate students training them for careers in industry, government and academia. Dr. Zhao is developing catalytic applications of late transition metal-based cyclometalation processes. Catalytically-relevant metallacycles are generated through nickel- and ruthenium-mediated C-H bond activation of ancillary ligands such as N-heterocyclic carbenes (NHCs) and aromatic N-H ketimines. Other target cyclometalation processes include rhodium- and ruthenium-mediated decarboxylation of arene- and heteroarenecarboxylic acids via chelation assistance. Results of structure-reactivity relationships of cyclometalated catalyst precursors and reactive intermediates are guiding new catalyst developments via atom-efficient activation of strong chemical bonds including carbon-hydrogen, oxygen-hydrogen, and carbon-carbon bonds. Dr. Zhao is also leading an initiative to develop a web-based searchable database to promote general dissemination of fundamental knowledge on chemical bond transformations in organometallic chemistry.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.