Ge, PeiyuOlaya, Astrid J.Scanlon, Micheál D.Hatay Patir, ImrenVrubel, HeronGirault, Hubert H.2013-05-202013-05-202013-05-20201310.1002/cphc.201300122https://infoscience.epfl.ch/handle/20.500.14299/92327WOS:000322236400040Excitation of the weak electron donor decamethylosmocene on illumination with white light produces an excited-state species capable of reducing organically solubilized protons under biphasic conditions. Insight into the mechanism and kinetics of light-driven biphasic hydrogen evolution are obtained by analysis with gas chromatography, cyclic voltammetry, and UV/Vis and 1H NMR spectroscopy. Formation of decamethylosmocenium hydride, which occurs prior to hydrogen evolution, is a rapid step relative to hydrogen release and takes place independently of light activation. Remarkably, hydride formation occurs with greater efficiency (ca. 90 % conversion) under biphasic conditions than when the reaction is carried out in an acidified single organic phase (ca. 20 % conversion). Cyclic voltammetry studies reveal that decamethylosmocene has a higher proton affinity than either decamethylferrocene or osmocene.electrochemistryhydrogen evolution reactioninterfacesmetallocenesphotochemistrytext::journal::journal article::research article