A Pseudotetrahedral Terminal Oxoiron(IV) Complex: Mechanistic Promiscuity in C−H Bond Oxidation Reactions

dc.contributor.authorWarm, Katrin
dc.contributor.authorPaskin, Alice
dc.contributor.authorKuhlmann, Uwe
dc.contributor.authorBill, Eckhard
dc.contributor.authorSwart, Marcel
dc.contributor.authorHaumann, Michael
dc.contributor.authorDau, Holger
dc.contributor.authorHildebrandt, Peter
dc.contributor.authorRay, Kallol
dc.date.accessioned2021-06-24T13:59:00Z
dc.date.available2021-06-24T13:59:00Z
dc.date.issued2021-02-15
dc.date.updated2021-06-01T10:55:27Z
dc.description.abstractS=2 oxoiron(IV) species act as reactive intermediates in the catalytic cycle of nonheme iron oxygenases. The few available synthetic S=2 FeIV=O complexes known to date are often limited to trigonal bipyramidal and very rarely to octahedral geometries. Herein we describe the generation and characterization of an S=2 pseudotetrahedral FeIV=O complex 2 supported by the sterically demanding 1,4,7‐tri‐tert‐butyl‐1,4,7‐triazacyclononane ligand. Complex 2 is a very potent oxidant in hydrogen atom abstraction (HAA) reactions with large non‐classical deuterium kinetic isotope effects, suggesting hydrogen tunneling contributions. For sterically encumbered substrates, direct HAA is impeded and an alternative oxidative asynchronous proton‐coupled electron transfer mechanism prevails, which is unique within the nonheme oxoiron community. The high reactivity and the similar spectroscopic parameters make 2 one of the best electronic and functional models for a biological oxoiron(IV) intermediate of taurine dioxygenase (TauD‐J).en
dc.description.sponsorshipDFG, 390540038, EXC 2008: Unifying Systems in Catalysis "UniSysCat"en
dc.identifier.eissn1521-3773
dc.identifier.issn1433-7851
dc.identifier.urihttps://depositonce.tu-berlin.de/handle/11303/13281
dc.identifier.urihttp://dx.doi.org/10.14279/depositonce-12073
dc.language.isoenen
dc.rights.urihttps://creativecommons.org/licenses/by-nc-nd/4.0/en
dc.subject.ddc540 Chemie und zugeordnete Wissenschaftende
dc.subject.otherbioinorganic chemistryen
dc.subject.otherenzyme modelsen
dc.subject.otherhigh-valent ironen
dc.subject.otherhydrogen atom abstractionen
dc.subject.otherelectron transferen
dc.titleA Pseudotetrahedral Terminal Oxoiron(IV) Complex: Mechanistic Promiscuity in C−H Bond Oxidation Reactionsen
dc.typeArticleen
dc.type.versionpublishedVersionen
dcterms.bibliographicCitation.doi10.1002/anie.202015896en
dcterms.bibliographicCitation.issue12en
dcterms.bibliographicCitation.journaltitleAngewandte Chemieen
dcterms.bibliographicCitation.originalpublishernameWileyen
dcterms.bibliographicCitation.originalpublisherplaceNew York, NYen
dcterms.bibliographicCitation.pageend6756en
dcterms.bibliographicCitation.pagestart6752en
dcterms.bibliographicCitation.volume60en
tub.accessrights.dnbfreeen
tub.affiliationFak. 2 Mathematik und Naturwissenschaften>Inst. Chemie>FG Physikalische Chemie / Biophysikalische Chemiede
tub.affiliation.facultyFak. 2 Mathematik und Naturwissenschaftende
tub.affiliation.groupFG Physikalische Chemie / Biophysikalische Chemiede
tub.affiliation.instituteInst. Chemiede
tub.publisher.universityorinstitutionTechnische Universität Berlinen
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