Chalcogenide-capped triiron clusters [Fe3(CO)9(μ3-E)2], [Fe3(CO)7(μ3-CO)(μ3-E)(μ-dppm)] and [Fe3(CO)7(μ3-E)2(μ-dppm)] (E = S, Se) as proton-reduction catalysts
(2019) In Journal of Organometallic Chemistry 880. p.213-222- Abstract
Chalcogenide-capped triiron clusters [Fe3(CO)7(μ3-CO)(μ3-E)(μ-dppm)] and [Fe3(CO)7(μ3-E)2(μ-dppm)] (E = S, Se) have been examined as proton-reduction catalysts. Protonation studies show that [Fe3(CO)9(μ3-E)2] are unaffected by strong acids. Mono-capped [Fe3(CO)7(μ3-CO)(μ3-E)(μ-dppm)] react with HBF4.Et2O but changes in IR spectra are attributed to BF3 binding to the face-capping carbonyl, while bicapped [Fe3(CO)7(μ3-E)2(μ-dppm)] are protonated but in a process that is not catalytically... (More)
Chalcogenide-capped triiron clusters [Fe3(CO)7(μ3-CO)(μ3-E)(μ-dppm)] and [Fe3(CO)7(μ3-E)2(μ-dppm)] (E = S, Se) have been examined as proton-reduction catalysts. Protonation studies show that [Fe3(CO)9(μ3-E)2] are unaffected by strong acids. Mono-capped [Fe3(CO)7(μ3-CO)(μ3-E)(μ-dppm)] react with HBF4.Et2O but changes in IR spectra are attributed to BF3 binding to the face-capping carbonyl, while bicapped [Fe3(CO)7(μ3-E)2(μ-dppm)] are protonated but in a process that is not catalytically important. DFT calculations are presented to support these protonation studies. Cyclic voltammetry shows that [Fe3(CO)9(μ3-Se)2] exhibits two reduction waves, and upon addition of strong acids, proton-reduction occurs at a range of potentials. Mono-chalcogenide clusters [Fe3(CO)7(μ3-CO)(μ3-E)(μ-dppm)] (E = S, Se) exhibit proton-reduction at ca. -1.85 (E = S) and -1.62 V (E = Se) in the presence of p-toluene sulfonic acid (p-TsOH). Bicapped [Fe3(CO)7(μ3-E)2(μ-dppm)] undergo quasi-reversible reductions at -1.55 (E = S) and -1.45 V (E = Se) and reduce p-TsOH to hydrogen but protonated species do not appear to be catalytically important. Current uptake is seen at the first reduction potential in each case, showing that [Fe3(CO)7(μ3-E)2(μ-dppm)]- are catalytically active but a far greater response is seen at ca. -1.9 V being tentatively associated with reduction of [H2Fe3(CO)7(μ3-E)2(μ-dppm)]+. In general, selenide clusters are reduced at slightly lower potentials than sulfide analogues and show slightly higher current uptake under comparable conditions.
(Less)
- author
- Rahaman, Ahibur LU ; Ghosh, Shishir ; Basak-Modi, Sucharita ; Abdel-Magied, Ahmed F. ; Kabir, Shariff E. ; Haukka, Matti ; Richmond, Michael G. ; Lisensky, George C. LU ; Nordlander, Ebbe LU and Hogarth, Graeme
- organization
- publishing date
- 2019
- type
- Contribution to journal
- publication status
- published
- subject
- keywords
- Chalcogenide, Cluster, Electrochemistry, Proton-reduction, Triiron
- in
- Journal of Organometallic Chemistry
- volume
- 880
- pages
- 10 pages
- publisher
- Elsevier
- external identifiers
-
- scopus:85056623912
- ISSN
- 0022-328X
- DOI
- 10.1016/j.jorganchem.2018.10.018
- language
- English
- LU publication?
- yes
- id
- 7432758e-dbd7-4d86-8562-cb782e121c41
- date added to LUP
- 2018-11-26 11:55:22
- date last changed
- 2022-04-25 19:19:03
@article{7432758e-dbd7-4d86-8562-cb782e121c41,
abstract = {{<p>Chalcogenide-capped triiron clusters [Fe<sub>3</sub>(CO)<sub>7</sub>(μ<sub>3</sub>-CO)(μ<sub>3</sub>-E)(μ-dppm)] and [Fe<sub>3</sub>(CO)<sub>7</sub>(μ<sub>3</sub>-E)<sub>2</sub>(μ-dppm)] (E = S, Se) have been examined as proton-reduction catalysts. Protonation studies show that [Fe<sub>3</sub>(CO)<sub>9</sub>(μ<sub>3</sub>-E)<sub>2</sub>] are unaffected by strong acids. Mono-capped [Fe<sub>3</sub>(CO)<sub>7</sub>(μ<sub>3</sub>-CO)(μ<sub>3</sub>-E)(μ-dppm)] react with HBF<sub>4</sub>.Et<sub>2</sub>O but changes in IR spectra are attributed to BF<sub>3</sub> binding to the face-capping carbonyl, while bicapped [Fe<sub>3</sub>(CO)<sub>7</sub>(μ<sub>3</sub>-E)<sub>2</sub>(μ-dppm)] are protonated but in a process that is not catalytically important. DFT calculations are presented to support these protonation studies. Cyclic voltammetry shows that [Fe<sub>3</sub>(CO)<sub>9</sub>(μ<sub>3</sub>-Se)<sub>2</sub>] exhibits two reduction waves, and upon addition of strong acids, proton-reduction occurs at a range of potentials. Mono-chalcogenide clusters [Fe<sub>3</sub>(CO)<sub>7</sub>(μ<sub>3</sub>-CO)(μ<sub>3</sub>-E)(μ-dppm)] (E = S, Se) exhibit proton-reduction at ca. -1.85 (E = S) and -1.62 V (E = Se) in the presence of p-toluene sulfonic acid (p-TsOH). Bicapped [Fe<sub>3</sub>(CO)<sub>7</sub>(μ<sub>3</sub>-E)<sub>2</sub>(μ-dppm)] undergo quasi-reversible reductions at -1.55 (E = S) and -1.45 V (E = Se) and reduce p-TsOH to hydrogen but protonated species do not appear to be catalytically important. Current uptake is seen at the first reduction potential in each case, showing that [Fe<sub>3</sub>(CO)<sub>7</sub>(μ<sub>3</sub>-E)<sub>2</sub>(μ-dppm)]<sup>-</sup> are catalytically active but a far greater response is seen at ca. -1.9 V being tentatively associated with reduction of [H<sub>2</sub>Fe<sub>3</sub>(CO)<sub>7</sub>(μ<sub>3</sub>-E)<sub>2</sub>(μ-dppm)]<sup>+</sup>. In general, selenide clusters are reduced at slightly lower potentials than sulfide analogues and show slightly higher current uptake under comparable conditions.</p>}},
author = {{Rahaman, Ahibur and Ghosh, Shishir and Basak-Modi, Sucharita and Abdel-Magied, Ahmed F. and Kabir, Shariff E. and Haukka, Matti and Richmond, Michael G. and Lisensky, George C. and Nordlander, Ebbe and Hogarth, Graeme}},
issn = {{0022-328X}},
keywords = {{Chalcogenide; Cluster; Electrochemistry; Proton-reduction; Triiron}},
language = {{eng}},
pages = {{213--222}},
publisher = {{Elsevier}},
series = {{Journal of Organometallic Chemistry}},
title = {{Chalcogenide-capped triiron clusters [Fe<sub>3</sub>(CO)<sub>9</sub>(μ<sub>3</sub>-E)<sub>2</sub>], [Fe<sub>3</sub>(CO)<sub>7</sub>(μ<sub>3</sub>-CO)(μ<sub>3</sub>-E)(μ-dppm)] and [Fe<sub>3</sub>(CO)<sub>7</sub>(μ<sub>3</sub>-E)<sub>2</sub>(μ-dppm)] (E = S, Se) as proton-reduction catalysts}},
url = {{http://dx.doi.org/10.1016/j.jorganchem.2018.10.018}},
doi = {{10.1016/j.jorganchem.2018.10.018}},
volume = {{880}},
year = {{2019}},
}