Mechanistic Study on the Photogeneration of Hydrogen by Decamethylruthenocene

Tutkimustuotos: Lehtiartikkelivertaisarvioitu

Tutkijat

  • Lucie Rivier
  • Pekka Peljo

  • Sunny Maye
  • Manuel A. Méndez
  • Heron Vrubel
  • Laurent A.C. Vannay
  • Clémence Corminboeuf
  • Micheál D. Scanlon
  • Hubert H. Girault

Organisaatiot

  • University of Limerick
  • Ecole Polytechnique Federale de Lausanne
  • Centre for Marine and Renewable Energy Ireland

Kuvaus

Detailed studies on hydrogen evolution by decamethylruthenocene ([Cp*2 RuII ]) highlighted that metallocenes are capable of photoreducing hydrogen without the need for an additional sensitizer. Electrochemical, gas chromatographic, and spectroscopic (UV/Vis, 1 H and 13 C NMR) measurements corroborated by DFT calculations indicated that the production of hydrogen occurs by a two-step process. First, decamethylruthenocene hydride [Cp*2 RuIV (H)]+ is formed in the presence of an organic acid. Subsequently, [Cp*2 RuIV (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*2 RuIII ]+ is further reduced with a second release of hydrogen by deprotonation of a methyl group of [Cp*2 RuIII ]+ . Experimental and computational data show spontaneous conversion of [Cp*2 RuII ] to [Cp*2 RuIV (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*2 RuII ] was also considered.

Yksityiskohdat

AlkuperäiskieliEnglanti
Sivut12769-12779
Sivumäärä11
JulkaisuChemistry (Weinheim an der Bergstrasse, Germany)
Vuosikerta25
Numero55
TilaJulkaistu - 1 lokakuuta 2019
OKM-julkaisutyyppiA1 Julkaistu artikkeli, soviteltu

ID: 37669133