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
Rahaman, A., Ghosh, S., Basak-Modi, S., Abdel-Magied, A. F., Kabir, S. E., Haukka, M., Richmond, M. G., Lisensky, G. C., Nordlander, E., & Hogarth, G. (2019). 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. Journal of Organometallic Chemistry, 880, 213-222. https://doi.org/10.1016/j.jorganchem.2018.10.018
Published in
Journal of Organometallic ChemistryAuthors
Date
2019Copyright
© 2018 Elsevier B.V.
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.
...


Publisher
Elsevier BVISSN Search the Publication Forum
0022-328XPublication in research information system
https://converis.jyu.fi/converis/portal/detail/Publication/28697248
Metadata
Show full item recordCollections
License
Related items
Showing items with similar title or keywords.
-
Proton reduction by phosphinidene-capped triiron clusters
Rahaman, Ahibur; Lisensky, George C.; Haukka, Matti; Tocher, Derek A.; Richmond, Michael G.; Colbran, Stephen B.; Nordlander, Ebbe (Elsevier BV, 2021)Bis(phosphinidene)-capped triiron carbonyl clusters, including electron rich derivatives formed by substitution with chelating diphosphines, have been prepared and examined as proton reduction catalysts. Treatment of the ... -
Coadsorption of NRR and HER Intermediates Determines the Performance of Ru-N4 toward Electrocatalytic N2 Reduction
Wu, Tongwei; Melander, Marko M.; Honkala, Karoliina (American Chemical Society (ACS), 2022)Electrochemical N2 reduction (NRR) to ammonia is seriously limited by the competing hydrogen evolution reaction (HER), but atomic-scale factors controlling HER/NRR competition are unknown. Herein we unveil the mechanism, ... -
H2-TPR, XPS and TEM Study of the Reduction of Ru and Re promoted Co/γ-Al2O3, Co/TiO2 and Co/SiC Catalysts
Romar, H.; Lillebø, A. H.; Tynjälä, Pekka; Hu, T.; Holmen, A.; Blekkan, E. A.; Lassi, U. (Canadian Center of Science and Education, 2016)Effects of Ru and Re promoters on Co-CoOx catalysts supported on γ-Al2O3, TiO2 and SiC were investigated to improve the understanding of the role of promoters of the active phase of Co-CoOx-Ru and Co-CoOx-Re. The influence ... -
Advances and challenges for experiment and theory for multi-electron multi-proton transfer at electrified solid–liquid interfaces
Sakaushi, Ken; Kumeda, Tomoaki; Hammes-Schiffer, Sharon; Melander, Marko M.; Sugino, Osamu (Royal Society of Chemistry (RSC), 2020)Multi-electron, multi-proton transfer is important in a wide spectrum of processes spanning biological, chemical and physical systems. These reactions have attracted significant interest due to both fundamental curiosity ... -
Grand Canonical Rate Theory for Electrochemical and Electrocatalytic Systems I : General Formulation and Proton-coupled Electron Transfer Reactions
Melander, Marko M. (Electrochemical Society, 2020)Electrochemical interfaces present a serious challenge for atomistic modelling. Electrochemical thermodynamics are naturally addressed within the grand canonical ensemble (GCE) but the lack of a fixed potential rate theory ...