Electrocatalytic proton reduction by thiolate-capped triiron clusters [Fe3(CO)9(μ3-SR)(μ-H)] (R = iPr, tBu)
(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)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.... (More)
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.
(Less)
- author
- Ghosh, Shishir ; Basak-Modi, Sucharita ; Richmond, Michael G. ; Nordlander, Ebbe LU and Hogarth, Graeme
- organization
- publishing date
- 2018-08-01
- 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
- 2022-03-09 18:57:42
@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}}, keywords = {{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}}, doi = {{10.1016/j.ica.2018.04.034}}, volume = {{480}}, year = {{2018}}, }