Ge, PeiyuOlaya, Astrid J.Scanlon, Micheal D.Patir, Imren HatayVrubel, HeronGirault, Hubert H.2020-03-262020-03-2620131439-42351439-7641https://dx.doi.org/10.1002/cphc.201300122https://hdl.handle.net/20.500.12395/29727Excitation 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 H-1 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.en10.1002/cphc.201300122info:eu-repo/semantics/closedAccesselectrochemistryhydrogen evolution reactioninterfacesmetallocenesphotochemistryArticle14102308231623687064Q2WOS:000322236400040Q1