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dc.contributor.authorRahaman, Ahibur
dc.contributor.authorGhosh, Shishir
dc.contributor.authorBasak-Modi, Sucharita
dc.contributor.authorAbdel-Magied, Ahmed F.
dc.contributor.authorKabir, Shariff E.
dc.contributor.authorHaukka, Matti
dc.contributor.authorRichmond, Michael G.
dc.contributor.authorLisensky, George C.
dc.contributor.authorNordlander, Ebbe
dc.contributor.authorHogarth, Graeme
dc.date.accessioned2018-11-26T11:14:01Z
dc.date.available2021-02-01T22:35:10Z
dc.date.issued2019
dc.identifier.citationRahaman, 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. <i>Journal of Organometallic Chemistry</i>, <i>880</i>, 213-222. <a href="https://doi.org/10.1016/j.jorganchem.2018.10.018" target="_blank">https://doi.org/10.1016/j.jorganchem.2018.10.018</a>
dc.identifier.otherCONVID_28697248
dc.identifier.otherTUTKAID_79370
dc.identifier.urihttps://jyx.jyu.fi/handle/123456789/60340
dc.description.abstractChalcogenide-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.fi
dc.format.mimetypeapplication/pdf
dc.language.isoeng
dc.publisherElsevier BV
dc.relation.ispartofseriesJournal of Organometallic Chemistry
dc.rightsCC BY-NC-ND 4.0
dc.subject.othertriiron
dc.subject.otherchalcogenide
dc.subject.othercluster
dc.subject.otherproton-reduction
dc.titleChalcogenide-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
dc.typearticle
dc.identifier.urnURN:NBN:fi:jyu-201811194765
dc.contributor.laitosKemian laitosfi
dc.contributor.laitosDepartment of Chemistryen
dc.contributor.oppiaineEpäorgaaninen ja analyyttinen kemiafi
dc.contributor.oppiaineInorganic and Analytical Chemistryen
dc.type.urihttp://purl.org/eprint/type/JournalArticle
dc.date.updated2018-11-19T07:15:11Z
dc.description.reviewstatuspeerReviewed
dc.format.pagerange213-222
dc.relation.issn0022-328X
dc.relation.numberinseries0
dc.relation.volume880
dc.type.versionacceptedVersion
dc.rights.copyright© 2018 Elsevier B.V.
dc.rights.accesslevelopenAccessfi
dc.subject.ysoorganometalliyhdisteet
dc.subject.ysosähkökemia
dc.format.contentfulltext
jyx.subject.urihttp://www.yso.fi/onto/yso/p28123
jyx.subject.urihttp://www.yso.fi/onto/yso/p8093
dc.rights.urlhttps://creativecommons.org/licenses/by-nc-nd/4.0/
dc.relation.doi10.1016/j.jorganchem.2018.10.018


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