期刊名称：Proceedings of the National Academy of Sciences
印刷版ISSN：0027-8424
电子版ISSN：1091-6490
出版年度：2016
卷号：113
期号：23
页码：6409-6414
DOI：10.1073/pnas.1606018113
语种：English
出版社：The National Academy of Sciences of the United States of America
摘要：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.
