Electrocatalytic proton reduction by thiolate-capped triiron clusters [Fe3(CO)93-SR)(μ-H)] (R = iPr, tBu)

Research output: Contribution to journalArticle

Abstract

The redox behaviour and electrocatalytic proton reduction ability of the thiolate-capped triiron clusters [Fe3(CO)93-SR)(μ-H)] (1, R = iPr; 2, R = tBu) have been investigated. In CH2Cl2, both show a quasi-reversible reduction and an irreversible oxidation. The thiol substituent has a significant influence on their reduction potentials (E1/2 = −1.24 V for 1 and E1/2 = −1.40 V for 2 vs. Fc+/Fc) but less impact on oxidation potentials (E1/2 = 0.99 V for 1 and E1/2 = 0.93 V for 2 vs. Fc+/Fc). Reduction is quasi-reversible and DFT studies reveal that this is due to scission of an iron-iron bond. While the clusters are not protonated by CF3CO2H or HBF4·Et2O, they can catalyse proton reduction of these acids at their corresponding reduction potentials following an ECEC mechanism.

Details

Authors
  • Shishir Ghosh
  • Sucharita Basak-Modi
  • Michael G. Richmond
  • Ebbe Nordlander
  • Graeme Hogarth
Organisations
External organisations
  • University College London
  • King's College London
  • University of North Texas
Research areas and keywords

Subject classification (UKÄ) – MANDATORY

  • Inorganic Chemistry

Keywords

  • DFT studies, Electrocatalytic proton reduction, Thiolate, Triiron clusters
Original languageEnglish
Pages (from-to)47-53
Number of pages7
JournalInorganica Chimica Acta
Volume480
Publication statusPublished - 2018 Aug 1
Publication categoryResearch
Peer-reviewedYes