Catalytic, Regioselective Functionalization of Alkane and Arenes

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This award in the Inorganic, Bioinorganic and Organometallic Chemistry program supports research by Professor John F. Hartwig at Yale University to develop an iridium-catalyzed borylation of alkanes and a similar borylation of arenes with catecholborane to form more reactive arylboronate products and to conduct mechanistic experiments on iridium-catalyzed reactions of pinacolborane. Based on preliminary results gained with ruthenium catalysts and the reactivity of ruthenium boryl complexes toward alkanes, the true catalyst in the ruthenium-catalyzed borylation of alkanes will be identified and the electronic properties of metal-boryl complexes that promote C-H bond cleavage will be determined. Based on the PI's recent discovery of catalysts for the silylation of arenes, mild intramolecular silylations of arenes and alkanes with and without a hydrogen acceptor and more reactive catalysts for the intermolecular silylation of arenas will be developed. The origins of the regioselectivity for functionalization of terminal C-H bonds will be determined by conducting a series of deuterium labeling experiments that will distinguish between C-H bond cleavage and B-C bond formation as the step that controls regioselective functionalization of alkanes, amines, ethers and haloalkanes. The work described here will extend new methods of catalysis and help broaden the educational experiences of undergraduate, PhD and postdoctoral students. The PI mentors the summer research of several minority students as part of Yale's STARS program, endeavors to present his research to groups of high school students and other audiences, and is involved in writing the next edition of a textbook on transition metal chemistry.