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Mechanistic study of the photo-generation of hydrogen by decamethylruthenocene

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Show simple item record Rivier, Lucie Peljo, Pekka Maye, Sunny Méndez, Manuel A. Vrubel, Heron Vannay, Laurent A.C. Corminboeuf, Clémence Scanlon, Micheál D. Girault, Hubert H. 2020-01-14T15:37:12Z 2019
dc.description peer-reviewed en_US
dc.description The full text of this article will not be available in ULIR until the embargo expires on the 09/07/2020
dc.description.abstract Detailed studies on hydrogen evolution by decamethylruthenocene ([Cp*2RuII]) highlighted that metallocenes are capable of photoreducing hydrogen without the need for an additional sensitizer. Electrochemical, gas chromatographic, and spectroscopic (UV/Vis, 1H and 13C NMR) measurements corroborated by DFT calculations indicated that the production of hydrogen occurs by a two‐step process. First, decamethylruthenocene hydride [Cp*2RuIV(H)]+ is formed in the presence of an organic acid. Subsequently, [Cp*2RuIV(H)]+ is reversibly reduced in a heterolytic reaction with one‐photon excitation leading to a first release of hydrogen. Thereafter, the resultant decamethylruthenocenium ion [Cp*2RuIII]+ is further reduced with a second release of hydrogen by deprotonation of a methyl group of [Cp*2RuIII]+. Experimental and computational data show spontaneous conversion of [Cp*2RuII] to [Cp*2RuIV(H)]+ in the presence of protons. Calculations highlight that the first reduction is endergonic (ΔG0=108 kJ mol−1) and needs an input of energy by light for the reaction to occur. The hydricity of the methyl protons of [Cp*2RuII] was also considered. en_US
dc.language.iso eng en_US
dc.publisher Wiley and Sons Ltd en_US
dc.relation 716792 en_US
dc.relation.ispartofseries Chemistry: A European Journal;25 (55), pp. 12769-12779
dc.rights This is the author accepted peer reviewed version of the following article: Mechanistic study of the photo-generation of hydrogen by decamethylruthenocene,Chemistry: A European Journal;25 (55), pp. 12769-12779 , which has been published in final form at This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving. en_US
dc.subject hydrogen en_US
dc.title Mechanistic study of the photo-generation of hydrogen by decamethylruthenocene en_US
dc.type info:eu-repo/semantics/article en_US
dc.type.supercollection all_ul_research en_US
dc.type.supercollection ul_published_reviewed en_US 2020-01-10T15:04:17Z
dc.description.version ACCEPTED
dc.identifier.doi 10.1002/chem.201902353
dc.contributor.sponsor Swiss National Science Foundation en_US
dc.relation.projectid 200020 en_US
dc.relation.projectid 152557 en_US
dc.relation.projectid 20021-156001 en_US
dc.relation.projectid 716792 en_US
dc.relation.projectid 13/SIRG/2137 en_US 2020-07-09
dc.embargo.terms 2020-07-09 en_US
dc.rights.accessrights info:eu-repo/semantics/embargoedAccess en_US
dc.internal.rssid 2918029
dc.internal.copyrightchecked Yes
dc.identifier.journaltitle Chemistry A European Journal
dc.description.status peer-reviewed

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