doi:10.1002/anie.201610240 ISI:000395566600012 Rivier, Lucie Peljo, Pekka Eero Vannay, Laurent A. C. Gschwend, Grégoire Clément Méndez, Manuel A. Corminboeuf, Clémence Scanlon, Micheál D. Girault, Hubert Photoproduction of Hydrogen by Decamethylruthenocene Combined with Electrochemical Recycling Weinheim, Wiley-Blackwell The photoinduced hydrogen evolution reaction (HER) by decamethylruthenocene, Cp2*RuII (Cp*=C5Me5), is reported. The use of a metallocene to photoproduce hydrogen is presented as an alternative strategy to reduce protons without involving an additional photosensitizer. The mechanism was investigated by (spectro)electrochemical and spectroscopic (UV/Vis and 1H NMR) measurements. The photoactivated hydride involved was characterized spectroscopically and the resulting [Cp2*RuIII]+ species was electrochemically regenerated in situ on a fluorinated tin oxide electrode surface. A promising internal quantum yield of 25 % was obtained. Optimal experimental conditions— especially the use of weakly coordinating solvent and counterions—are discussed. 2017-01-27T13:30:16Z Text