A Pseudotetrahedral Terminal Oxoiron(IV) Complex: Mechanistic Promiscuity in C−H Bond Oxidation Reactions
| dc.contributor.author | Warm, Katrin | |
| dc.contributor.author | Paskin, Alice | |
| dc.contributor.author | Kuhlmann, Uwe | |
| dc.contributor.author | Bill, Eckhard | |
| dc.contributor.author | Swart, Marcel | |
| dc.contributor.author | Haumann, Michael | |
| dc.contributor.author | Dau, Holger | |
| dc.contributor.author | Hildebrandt, Peter | |
| dc.contributor.author | Ray, Kallol | |
| dc.date.accessioned | 2021-06-24T13:59:00Z | |
| dc.date.available | 2021-06-24T13:59:00Z | |
| dc.date.issued | 2021-02-15 | |
| dc.date.updated | 2021-06-01T10:55:27Z | |
| dc.description.abstract | S=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.sponsorship | DFG, 390540038, EXC 2008: Unifying Systems in Catalysis "UniSysCat" | en |
| dc.identifier.eissn | 1521-3773 | |
| dc.identifier.issn | 1433-7851 | |
| dc.identifier.uri | https://depositonce.tu-berlin.de/handle/11303/13281 | |
| dc.identifier.uri | http://dx.doi.org/10.14279/depositonce-12073 | |
| dc.language.iso | en | en |
| dc.rights.uri | https://creativecommons.org/licenses/by-nc-nd/4.0/ | en |
| dc.subject.ddc | 540 Chemie und zugeordnete Wissenschaften | de |
| dc.subject.other | bioinorganic chemistry | en |
| dc.subject.other | enzyme models | en |
| dc.subject.other | high-valent iron | en |
| dc.subject.other | hydrogen atom abstraction | en |
| dc.subject.other | electron transfer | en |
| dc.title | A Pseudotetrahedral Terminal Oxoiron(IV) Complex: Mechanistic Promiscuity in C−H Bond Oxidation Reactions | en |
| dc.type | Article | en |
| dc.type.version | publishedVersion | en |
| dcterms.bibliographicCitation.doi | 10.1002/anie.202015896 | en |
| dcterms.bibliographicCitation.issue | 12 | en |
| dcterms.bibliographicCitation.journaltitle | Angewandte Chemie | en |
| dcterms.bibliographicCitation.originalpublishername | Wiley | en |
| dcterms.bibliographicCitation.originalpublisherplace | New York, NY | en |
| dcterms.bibliographicCitation.pageend | 6756 | en |
| dcterms.bibliographicCitation.pagestart | 6752 | en |
| dcterms.bibliographicCitation.volume | 60 | en |
| tub.accessrights.dnb | free | en |
| tub.affiliation | Fak. 2 Mathematik und Naturwissenschaften::Inst. Chemie::FG Physikalische Chemie / Biophysikalische Chemie | de |
| tub.affiliation.faculty | Fak. 2 Mathematik und Naturwissenschaften | de |
| tub.affiliation.group | FG Physikalische Chemie / Biophysikalische Chemie | de |
| tub.affiliation.institute | Inst. Chemie | de |
| tub.publisher.universityorinstitution | Technische Universität Berlin | en |