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

Research output: Contribution to journalArticle


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.


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

Subject classification (UKÄ) – MANDATORY

  • Inorganic Chemistry


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