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

Ghosh, Shishir; Basak-Modi, Sucharita; Richmond, Michael G.; Nordlander, Ebbe LU and Hogarth, Graeme (2018) In Inorganica Chimica Acta 480. p.47-53
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.... (More)

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.

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organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
DFT studies, Electrocatalytic proton reduction, Thiolate, Triiron clusters
in
Inorganica Chimica Acta
volume
480
pages
7 pages
publisher
Elsevier
external identifiers
  • scopus:85047102704
ISSN
0020-1693
DOI
10.1016/j.ica.2018.04.034
language
English
LU publication?
yes
id
74906496-4b3a-4a9f-9b2d-b46cb48bb759
date added to LUP
2018-05-29 13:26:54
date last changed
2019-10-08 03:30:08
@article{74906496-4b3a-4a9f-9b2d-b46cb48bb759,
  abstract     = {<p>The redox behaviour and electrocatalytic proton reduction ability of the thiolate-capped triiron clusters [Fe<sub>3</sub>(CO)<sub>9</sub>(μ<sub>3</sub>-SR)(μ-H)] (1, R = <sup>i</sup>Pr; 2, R = <sup>t</sup>Bu) have been investigated. In CH<sub>2</sub>Cl<sub>2</sub>, both show a quasi-reversible reduction and an irreversible oxidation. The thiol substituent has a significant influence on their reduction potentials (E<sub>1/2</sub> = −1.24 V for 1 and E<sub>1/2</sub> = −1.40 V for 2 vs. Fc<sup>+</sup>/Fc) but less impact on oxidation potentials (E<sub>1/2</sub> = 0.99 V for 1 and E<sub>1/2</sub> = 0.93 V for 2 vs. Fc<sup>+</sup>/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 CF<sub>3</sub>CO<sub>2</sub>H or HBF<sub>4</sub>·Et<sub>2</sub>O, they can catalyse proton reduction of these acids at their corresponding reduction potentials following an ECEC mechanism.</p>},
  author       = {Ghosh, Shishir and Basak-Modi, Sucharita and Richmond, Michael G. and Nordlander, Ebbe and Hogarth, Graeme},
  issn         = {0020-1693},
  keyword      = {DFT studies,Electrocatalytic proton reduction,Thiolate,Triiron clusters},
  language     = {eng},
  month        = {08},
  pages        = {47--53},
  publisher    = {Elsevier},
  series       = {Inorganica Chimica Acta},
  title        = {Electrocatalytic proton reduction by thiolate-capped triiron clusters [Fe<sub>3</sub>(CO)<sub>9</sub>(μ<sub>3</sub>-SR)(μ-H)] (R = <sup>i</sup>Pr, <sup>t</sup>Bu)},
  url          = {http://dx.doi.org/10.1016/j.ica.2018.04.034},
  volume       = {480},
  year         = {2018},
}