PNNL

Abstract

Heterolytic cleavage of the H-H bond of H2 into a proton and hydride is a fundamentally important step in reactions of hydrogenase enzymes, oxidation of hydrogen in fuel cells, and catalytic hydrogenation of organic compounds. Incorporation of a pendant amine as a proton acceptor has been shown to facilitate reactions of the [FeFe]-hydrogenase enzyme as well as synthetic catalysts for oxidation of H2. We report the facile, reversible heterolytic cleavage of H2 in a Mn complex bearing a pendant amine, leading to an Mn-H and N-H bond, with an estimated rate of >107 s-1 at 25 ºC. We thank the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences, for support of the initial parts of this work. Current work is supported by the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.