Vibrational characterization of a diiron bridging hydride complex – a model for hydrogen catalysis

dc.contributor.authorGee, Leland B.
dc.contributor.authorPelmenschikov, Vladimir
dc.contributor.authorWang, Hongxin
dc.contributor.authorMishra, Nakul
dc.contributor.authorLiu, Yu-Chiao
dc.contributor.authorYoda, Yoshitaka
dc.contributor.authorTamasaku, Kenji
dc.contributor.authorChiang, Ming-Hsi
dc.contributor.authorCramer, Stephen P.
dc.date.accessioned2021-06-10T07:20:58Z
dc.date.available2021-06-10T07:20:58Z
dc.date.issued2020-05-06
dc.description.abstractA diiron complex containing a bridging hydride and a protonated terminal thiolate of the form [(μ,κ2-bdtH)(μ-PPh2)(μ-H)Fe2(CO)5]+ has been investigated through 57Fe nuclear resonance vibrational spectroscopy (NRVS) and interpreted using density functional theory (DFT) calculations. We report the Fe–μH–Fe wagging mode, and indications for Fe–μD stretching vibrations in the D-isotopologue, observed by 57Fe-NRVS. Our combined approach demonstrates an asymmetric sharing of the hydride between the two iron sites that yields two nondegenerate Fe–μH/D stretching vibrations. The studied complex provides an important model relevant to biological hydrogen catalysis intermediates. The complex mimics proposals for the binuclear metal sites in [FeFe] and [NiFe] hydrogenases. It is also an appealing prototype for the ‘Janus intermediate’ of nitrogenase, which has been proposed to contain two bridging Fe–H–Fe hydrides and two protonated sulfurs at the FeMo-cofactor. The significance of observing indirect effects of the bridging hydride, as well as obstacles in its direct observation, is discussed in the context of biological hydrogen intermediates.en
dc.description.sponsorshipDFG, 390540038, EXC 2008: Unifying Systems in Catalysis "UniSysCat"en
dc.identifier.eissn2041-6539
dc.identifier.issn2041-6520
dc.identifier.urihttps://depositonce.tu-berlin.de/handle/11303/13230
dc.identifier.urihttp://dx.doi.org/10.14279/depositonce-12025
dc.language.isoenen
dc.rights.urihttps://creativecommons.org/licenses/by-nc/3.0/en
dc.subject.ddc540 Chemie und zugeordnete Wissenschaftende
dc.subject.otherhydride complexen
dc.subject.otherhydrogen catalysisen
dc.subject.otherdiiron complexen
dc.titleVibrational characterization of a diiron bridging hydride complex – a model for hydrogen catalysisen
dc.typeArticleen
dc.type.versionpublishedVersionen
dcterms.bibliographicCitation.doi10.1039/D0SC01290Den
dcterms.bibliographicCitation.issue21en
dcterms.bibliographicCitation.journaltitleChemical Scienceen
dcterms.bibliographicCitation.originalpublishernameRoyal Society of Chemistryen
dcterms.bibliographicCitation.originalpublisherplaceCambridgeen
dcterms.bibliographicCitation.pageend5493en
dcterms.bibliographicCitation.pagestart5487en
dcterms.bibliographicCitation.volume11en
tub.accessrights.dnbfreeen
tub.affiliationFak. 2 Mathematik und Naturwissenschaften>Inst. Chemie>FG Theoretische Chemie - Quantenchemiede
tub.affiliation.facultyFak. 2 Mathematik und Naturwissenschaftende
tub.affiliation.groupFG Theoretische Chemie - Quantenchemiede
tub.affiliation.instituteInst. Chemiede
tub.publisher.universityorinstitutionTechnische Universität Berlinen
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