O−O Bond Formation and Liberation of Dioxygen Mediated by N5‐Coordinate Non‐Heme Iron(IV) Complexes

dc.contributor.authorKroll, Nicole
dc.contributor.authorSpeckmann, Ina
dc.contributor.authorSchoknecht, Marc
dc.contributor.authorGülzow, Jana
dc.contributor.authorDiekmann, Marek
dc.contributor.authorPfrommer, Johannes
dc.contributor.authorStritt, Anika
dc.contributor.authorSchlangen, Maria
dc.contributor.authorGrohmann, Andreas
dc.contributor.authorHörner, Gerald
dc.date.accessioned2020-02-13T16:40:12Z
dc.date.available2020-02-13T16:40:12Z
dc.date.issued2019-08-13
dc.description.abstractFormation of the O−O bond is considered the critical step in oxidative water cleavage to produce dioxygen. High‐valent metal complexes with terminal oxo (oxido) ligands are commonly regarded as instrumental for oxygen evolution, but direct experimental evidence is lacking. Herein, we describe the formation of the O−O bond in solution, from non‐heme, N5‐coordinate oxoiron(IV) species. Oxygen evolution from oxoiron(IV) is instantaneous once meta‐chloroperbenzoic acid is administered in excess. Oxygen‐isotope labeling reveals two sources of dioxygen, pointing to mechanistic branching between HAT (hydrogen atom transfer)‐initiated free‐radical pathways of the peroxides, which are typical of catalase‐like reactivity, and iron‐borne O−O coupling, which is unprecedented for non‐heme/peroxide systems. Interpretation in terms of [FeIV(O)] and [FeV(O)] being the resting and active principles of the O−O coupling, respectively, concurs with fundamental mechanistic ideas of (electro‐) chemical O−O coupling in water oxidation catalysis (WOC), indicating that central mechanistic motifs of WOC can be mimicked in a catalase/peroxidase setting.en
dc.description.sponsorshipDFG, 12489635, SFB 658: Elementarprozesse in molekularen Schaltern auf Oberflächenen
dc.description.sponsorshipTU Berlin, Open-Access-Mittel - 2019en
dc.identifier.eissn1521-3773
dc.identifier.issn1433-7851
dc.identifier.urihttps://depositonce.tu-berlin.de/handle/11303/10775
dc.identifier.urihttp://dx.doi.org/10.14279/depositonce-9670
dc.language.isoenen
dc.rights.urihttps://creativecommons.org/licenses/by/4.0/en
dc.subject.ddc540 Chemie und zugeordnete Wissenschaftende
dc.subject.otherbioinorganic chemistryen
dc.subject.otherironen
dc.subject.othernitrogen ligandsen
dc.subject.otherO−O activationen
dc.subject.otheroxo ligandsen
dc.titleO−O Bond Formation and Liberation of Dioxygen Mediated by N5‐Coordinate Non‐Heme Iron(IV) Complexesen
dc.typeArticleen
dc.type.versionpublishedVersionen
dcterms.bibliographicCitation.doi10.1002/anie.201903902en
dcterms.bibliographicCitation.issue38en
dcterms.bibliographicCitation.journaltitleAngewandte Chemie International Editionen
dcterms.bibliographicCitation.originalpublishernameWileyen
dcterms.bibliographicCitation.originalpublisherplaceWeinheimen
dcterms.bibliographicCitation.pageend13478en
dcterms.bibliographicCitation.pagestart13472en
dcterms.bibliographicCitation.volume58en
tub.accessrights.dnbfreeen
tub.affiliationFak. 2 Mathematik und Naturwissenschaften::Inst. Chemie::FG Bioanorganische Chemiede
tub.affiliation.facultyFak. 2 Mathematik und Naturwissenschaftende
tub.affiliation.groupFG Bioanorganische Chemiede
tub.affiliation.instituteInst. Chemiede
tub.publisher.universityorinstitutionTechnische Universität Berlinen

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