dc.contributor.author
Warm, Katrin
dc.contributor.author
Kass, Dustin
dc.contributor.author
Haumann, Michael
dc.contributor.author
Dau, Holger
dc.contributor.author
Ray, Kallol
dc.date.accessioned
2022-03-31T14:03:42Z
dc.date.available
2022-03-31T14:03:42Z
dc.identifier.uri
https://refubium.fu-berlin.de/handle/fub188/34175
dc.identifier.uri
http://dx.doi.org/10.17169/refubium-33893
dc.description.abstract
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.
en
dc.format.extent
7 Seiten
dc.rights.uri
https://creativecommons.org/licenses/by-nc/4.0/
dc.subject
Non-heme ligand
en
dc.subject
iron oxygenases
en
dc.subject
model complexes
en
dc.subject
oxoiron(IV) intermediate
en
dc.subject
O2-activation
en
dc.subject.ddc
500 Naturwissenschaften und Mathematik::540 Chemie::540 Chemie und zugeordnete Wissenschaften
dc.title
Modelling the coordination environment in α-ketoglutarate dependent oxygenases – a comparative study on the effect of N- vs. O-ligation
dc.type
Wissenschaftlicher Artikel
dcterms.bibliographicCitation.articlenumber
e202100310
dcterms.bibliographicCitation.doi
10.1002/zaac.202100310
dcterms.bibliographicCitation.journaltitle
Zeitschrift für anorganische und allgemeine Chemie
dcterms.bibliographicCitation.number
6
dcterms.bibliographicCitation.volume
648
dcterms.bibliographicCitation.url
https://doi.org/10.1002/zaac.202100310
refubium.affiliation
Physik
refubium.resourceType.isindependentpub
no
dcterms.accessRights.openaire
open access
dcterms.isPartOf.eissn
1521-3749
refubium.resourceType.provider
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