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Mechanistic study of the photo-generation of hydrogen by decamethylruthenocene

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dc.contributor.author Rivier, Lucie
dc.contributor.author Peljo, Pekka
dc.contributor.author Maye, Sunny
dc.contributor.author Méndez, Manuel A.
dc.contributor.author Vrubel, Heron
dc.contributor.author Vannay, Laurent A.C.
dc.contributor.author Corminboeuf, Clémence
dc.contributor.author Scanlon, Micheál D.
dc.contributor.author Girault, Hubert H.
dc.date.accessioned 2020-01-14T15:37:12Z
dc.date.issued 2019
dc.identifier.uri http://hdl.handle.net/10344/8373
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.relation.uri https://onlinelibrary.wiley.com/doi/abs/10.1002/chem.201902353
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 https://doi.org/10.1002/chem.201902353 This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving. http://olabout.wiley.com/WileyCDA/Section/id-828039.html#terms 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
dc.date.updated 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
dc.date.embargoEndDate 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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