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Ebbe Nordlander. Portrait.

Ebbe Nordlander

Professor

Ebbe Nordlander. Portrait.

Electrocatalytic proton reduction by thiolate-capped triiron clusters [Fe3(CO)9(μ3-SR)(μ-H)] (R = iPr, tBu)

Author

  • Shishir Ghosh
  • Sucharita Basak-Modi
  • Michael G. Richmond
  • Ebbe Nordlander
  • Graeme Hogarth

Summary, in English

The redox behaviour and electrocatalytic proton reduction ability of the thiolate-capped triiron clusters [Fe3(CO)9(μ3-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.

Department/s

  • Chemical Physics

Publishing year

2018-08-01

Language

English

Pages

47-53

Publication/Series

Inorganica Chimica Acta

Volume

480

Document type

Journal article

Publisher

Elsevier

Topic

  • Inorganic Chemistry

Keywords

  • DFT studies
  • Electrocatalytic proton reduction
  • Thiolate
  • Triiron clusters

Status

Published

ISBN/ISSN/Other

  • ISSN: 0020-1693