id,collection,dc.contributor.author,dc.date.accessioned,dc.date.available,dc.date.issued,dc.description.abstract[en],dc.format.extent,dc.identifier.uri,dc.language,dc.rights.uri,dc.subject.ddc,dc.subject[en],dc.title,dc.type,dcterms.accessRights.openaire,dcterms.bibliographicCitation.articlenumber,dcterms.bibliographicCitation.doi,dcterms.bibliographicCitation.journaltitle,dcterms.bibliographicCitation.number,dcterms.bibliographicCitation.url,dcterms.bibliographicCitation.volume,dcterms.isPartOf.eissn,refubium.affiliation,refubium.resourceType.isindependentpub,refubium.resourceType.provider "3cab4fa8-e17b-4806-93b7-2f5c8b0a77ad","fub188/16","Warm, Katrin||Kass, Dustin||Haumann, Michael||Dau, Holger||Ray, Kallol","2022-03-31T14:03:42Z","2022-03-31T14:03:42Z","2022","In various non-heme iron oxygenases the Fe(II) center is coordinated by 2 N and 1 O atoms of the 2-His-2-carboxylate facial triad; however, most artificial model complexes bear only N-based ligands. In an effort to closely mimic the coordination environment in α-ketoglutarate dependent oxygenases, we have now employed the Me2tacnO ligand (4,7-dimethyl-1-oxa-4,7-diazacyclononane) in the synthesis of the complexes [(Me2tacnO)FeCl2]2 (1-NNO), [(Me2tacnO)FeCl3] (1 b-NNO) and [(Me2tacnO)Fe(BF)Cl] (2-NNO; BF=benzoylformate). The weaker donation of the O atom in the ligand was found to result in stronger binding of the ligand in trans-position to the O-atom of the ancillary ligand as compared to the corresponding complexes involving the Me3tacn (1,4,7-trimethyl-1,4,7-triazacyclononane) ligand. Furthermore, by stopped-flow techniques we could detect an intermediate (3-NNO) in the reaction of 2-NNO with O2. The spectroscopic features of 3-NNO agree with the involvement of an Fe(IV)-oxo intermediate and hence this study represents the first detection of such an intermediate in the O2 activation of artificial α-ketoglutarate Fe(II) complexes.","7 Seiten","https://refubium.fu-berlin.de/handle/fub188/34175||http://dx.doi.org/10.17169/refubium-33893","eng","https://creativecommons.org/licenses/by-nc/4.0/","500 Naturwissenschaften und Mathematik::540 Chemie::540 Chemie und zugeordnete Wissenschaften","Non-heme ligand||iron oxygenases||model complexes||oxoiron(IV) intermediate||O2-activation","Modelling the coordination environment in α-ketoglutarate dependent oxygenases – a comparative study on the effect of N- vs. O-ligation","Wissenschaftlicher Artikel","open access","e202100310","10.1002/zaac.202100310","Zeitschrift für anorganische und allgemeine Chemie","6","https://doi.org/10.1002/zaac.202100310","648","1521-3749","Physik","no","WoS-Alert"