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Proton–hydride tautomerism in hydrogen evolution catalysis

Aguirre Quintana, Luis M. and Johnson, Samantha I. and Corona, Sydney L. and Villatoro, Walther and Goddard, William A., III and Takase, Michael K. and VanderVelde, David G. and Winkler, Jay R. and Gray, Harry B. and Blakemore, James D. (2016) Proton–hydride tautomerism in hydrogen evolution catalysis. Proceedings of the National Academy of Sciences of the United States of America, 113 (23). pp. 6409-6414. ISSN 0027-8424. PMCID PMC4988566. doi:10.1073/pnas.1606018113.

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Efficient generation of hydrogen from renewable resources requires development of catalysts that avoid deep wells and high barriers. Information about the energy landscape for H_2 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^+ → H_2 catalysis. This intermediate, obtained by treatment of Cp*Rh(bpy) (Cp*, η^5-pentamethylcyclopentadienyl; bpy, κ^2-2,2′-bipyridyl) with acid, is not a hydride species but rather, bears [η^4-Cp*H] as a ligand. Delivery of a second proton to this species leads to evolution of H_2 and reformation of η^5-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 H_2.

Item Type:Article
Related URLs:
URLURL TypeDescription Information CentralArticle
Aguirre Quintana, Luis M.0000-0003-0736-415X
Johnson, Samantha I.0000-0001-6495-9892
Corona, Sydney L.0000-0002-4962-619X
Goddard, William A., III0000-0003-0097-5716
Takase, Michael K.0000-0001-8365-3645
VanderVelde, David G.0000-0002-2907-0366
Winkler, Jay R.0000-0002-4453-9716
Gray, Harry B.0000-0002-7937-7876
Blakemore, James D.0000-0003-4172-7460
Additional Information:© 2016 National Academy of Sciences. Contributed by Harry B. Gray, April 17, 2016 (sent for review February 4, 2016; reviewed by Alexander Miller and David Milstein). Published online before print May 24, 2016. S.I.J. thanks Dr. Robert Nielsen for helpful discussions. This research, which was carried out in part at the Molecular Materials Research Center and the Laser Resource Center of the Beckman Institute (California Institute of Technology), was supported by NSF CCI Solar Fuels Program CHE-1305124. S.I.J. and J.D.B. acknowledge fellowships from the Resnick Sustainability Institute at Caltech. Author contributions: S.I.J., D.G.V., J.R.W., H.B.G., and J.D.B. designed research; L.M.A.Q., S.I.J., S.L.C., W.V., M.K.T., and J.D.B. performed research; W.A.G. contributed new reagents/analytic tools; L.M.A.Q., S.I.J., S.L.C., W.V., M.K.T., D.G.V., J.R.W., H.B.G., and J.D.B. analyzed data; and S.I.J., J.R.W., H.B.G., and J.D.B. wrote the paper. Reviewers: A.M., University of North Carolina; and D.M., The Weizmann Institute of Science. The authors declare no conflict of interest. Data deposition: The atomic coordinates and structure factors have been deposited in the Cambridge Crystallographic Data Centre (accession no. 1424707). This article contains supporting information online at
Group:Resnick Sustainability Institute, CCI Solar Fuels
Funding AgencyGrant Number
Resnick Sustainability InstituteUNSPECIFIED
Issue or Number:23
PubMed Central ID:PMC4988566
Record Number:CaltechAUTHORS:20160525-080847791
Persistent URL:
Official Citation:Luis M. Aguirre Quintana, Samantha I. Johnson, Sydney L. Corona, Walther Villatoro, William A. Goddard III, Michael K. Takase, David G. VanderVelde, Jay R. Winkler, Harry B. Gray, and James D. Blakemore Proton–hydride tautomerism in hydrogen evolution catalysis PNAS 2016 113 (23) 6409-6414; published ahead of print May 24, 2016, doi:10.1073/pnas.1606018113
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:67333
Deposited By: Tony Diaz
Deposited On:25 May 2016 17:27
Last Modified:27 Apr 2022 22:37

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