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Proton – hydride tautomerism in hydrogen evolution catalysis
Quintana, Luis M. Aguirre Johnson, Samantha I. Corona, Sydney L. Villatoro, Walther Goddard, William A., III Takase, Michael K. VanderVelde, David G. Winkler, Jay R. Gray, Harry B. Blakemore, James D.
Quintana, Luis M. Aguirre
Johnson, Samantha I.
Corona, Sydney L.
Villatoro, Walther
Goddard, William A., III
Takase, Michael K.
VanderVelde, David G.
Winkler, Jay R.
Gray, Harry B.
Blakemore, James D.
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Abstract
Efficient generation of hydrogen from renewable resources requires development of catalysts that avoid deep wells and high barriers. Information about the energy landscape for H2 production can be obtained by chemical characterization of catalytic intermediates, but few have been observed to date. We have isolated and characterized a key intermediate in 2e– + 2H+ → H2 catalysis. This intermediate, obtained by treatment of Cp*Rh(bpy) (Cp*, η5-pentamethylcyclopentadienyl; bpy, κ2-2,2′-bipyridyl) with acid, is not a hydride species but rather, bears [η4-Cp*H] as a ligand. Delivery of a second proton to this species leads to evolution of H2 and reformation of η5-Cp* bound to rhodium(III). With suitable choices of acids and bases, the Cp*Rh(bpy) complex catalyzes facile and reversible interconversion of H+ and H2.
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Date
2016-04-17
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Publisher
American Society for Biochemistry and Molecular Biology
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Keywords
Hydrogen evolution, Rhodium, Pentamethylcyclopentadienyl, Catalysis, Proton reduction
Citation
Quintana, L. M. A., Johnson, S. I., Corona, S. L., Villatoro, W., Goddard, W. A., Takase, M. K., ... & Blakemore, J. D. (2016). Proton–hydride tautomerism in hydrogen evolution catalysis. Proceedings of the National Academy of Sciences, 113(23), 6409-6414.