Binding of molecular oxygen by an artificial heme analogue: investigation on the formation of an Fe–tetracarbene superoxo complex

Handle URI:
http://hdl.handle.net/10754/601383
Title:
Binding of molecular oxygen by an artificial heme analogue: investigation on the formation of an Fe–tetracarbene superoxo complex
Authors:
Anneser, Markus R.; Haslinger, Stefan; Pöthig, Alexander; Cokoja, Mirza; D'Elia, Valerio; Högerl, Manuel P.; Basset, Jean-Marie ( 0000-0003-3166-8882 ) ; Kühn, Fritz E.
Abstract:
The dioxygen reactivity of a cyclic iron(II) tetra–NHC-complex (NHC: N-heterocyclic carbene) is investigated. Divergent oxidation behavior is observed depending on the choice of the solvent (acetonitrile or acetone). In the first case, exposure to molecular oxygen leads to an oxygen free Fe(III) whereas in the latter case an oxide bridged Fe(III) dimer is formed. In acetone, an Fe(III)-superoxide can be trapped, isolated and characterized as intermediate at low temperatures. An Fe(III)–O–Fe(III) dimer is formed from the Fe(III) superoxide in acetone upon warming and the molecular structure has been revealed by single crystal X-ray diffraction. It is shown that the oxidation of the Fe(II) complex in both solvents is a reversible process. For the regeneration of the initial Fe(II) complex both organic and inorganic reducing agents can be used.
KAUST Department:
KAUST Catalysis Center (KCC)
Citation:
Binding of molecular oxygen by an artificial heme analogue: investigation on the formation of an Fe–tetracarbene superoxo complex 2016 Dalton Trans.
Publisher:
Royal Society of Chemistry (RSC)
Journal:
Dalton Trans.
Issue Date:
26-Feb-2016
DOI:
10.1039/C6DT00538A
Type:
Article
ISSN:
1477-9226; 1477-9234
Sponsors:
M. R. A. and S. H. gratefully acknowledge support by the TUM Graduate School. This project was supported through a collaboration with the King Abdullah University of Saudi-Arabia (Grant No. KSA-C0069/UKC0020).
Is Supplemented By:
Anneser, M. R., Haslinger, S., Pöthig, A., Cokoja, M., D’Elia, V., Högerl, M. P., … Kühn, F. E. (2016). CCDC 1428063: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc1jy0k1; DOI:10.5517/cc1jy0k1; HANDLE:http://hdl.handle.net/10754/624473
Additional Links:
http://xlink.rsc.org/?DOI=C6DT00538A
Appears in Collections:
Articles; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorAnneser, Markus R.en
dc.contributor.authorHaslinger, Stefanen
dc.contributor.authorPöthig, Alexanderen
dc.contributor.authorCokoja, Mirzaen
dc.contributor.authorD'Elia, Valerioen
dc.contributor.authorHögerl, Manuel P.en
dc.contributor.authorBasset, Jean-Marieen
dc.contributor.authorKühn, Fritz E.en
dc.date.accessioned2016-03-16T13:51:37Zen
dc.date.available2016-03-16T13:51:37Zen
dc.date.issued2016-02-26en
dc.identifier.citationBinding of molecular oxygen by an artificial heme analogue: investigation on the formation of an Fe–tetracarbene superoxo complex 2016 Dalton Trans.en
dc.identifier.issn1477-9226en
dc.identifier.issn1477-9234en
dc.identifier.doi10.1039/C6DT00538Aen
dc.identifier.urihttp://hdl.handle.net/10754/601383en
dc.description.abstractThe dioxygen reactivity of a cyclic iron(II) tetra–NHC-complex (NHC: N-heterocyclic carbene) is investigated. Divergent oxidation behavior is observed depending on the choice of the solvent (acetonitrile or acetone). In the first case, exposure to molecular oxygen leads to an oxygen free Fe(III) whereas in the latter case an oxide bridged Fe(III) dimer is formed. In acetone, an Fe(III)-superoxide can be trapped, isolated and characterized as intermediate at low temperatures. An Fe(III)–O–Fe(III) dimer is formed from the Fe(III) superoxide in acetone upon warming and the molecular structure has been revealed by single crystal X-ray diffraction. It is shown that the oxidation of the Fe(II) complex in both solvents is a reversible process. For the regeneration of the initial Fe(II) complex both organic and inorganic reducing agents can be used.en
dc.description.sponsorshipM. R. A. and S. H. gratefully acknowledge support by the TUM Graduate School. This project was supported through a collaboration with the King Abdullah University of Saudi-Arabia (Grant No. KSA-C0069/UKC0020).en
dc.language.isoenen
dc.publisherRoyal Society of Chemistry (RSC)en
dc.relation.urlhttp://xlink.rsc.org/?DOI=C6DT00538Aen
dc.rightsArchived with thanks to Dalton Trans.en
dc.titleBinding of molecular oxygen by an artificial heme analogue: investigation on the formation of an Fe–tetracarbene superoxo complexen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.identifier.journalDalton Trans.en
dc.eprint.versionPost-printen
dc.contributor.institutionChair of Inorganic Chemistry/Molecular Catalysis, Catalysis Research Center, Ernst-Otto-Fischer-Strasse 1 and Faculty of Chemistry, Lichtenbergstrasse 4, Technische Universität München, D-85747 Garching bei München, Germanyen
dc.contributor.institutionDepartment of Materials Science and Engineering, School of Molecular Science and Engineering, Vidyasirimedhi Institute of Science and Technology, Wang Chan, Thailanden
dc.contributor.affiliationKing Abdullah University of Science and Technology (KAUST)en
kaust.authorD'Elia, Valerioen
kaust.authorHögerl, Manuel P.en
kaust.authorBasset, Jean-Marieen
dc.relation.isSupplementedByAnneser, M. R., Haslinger, S., Pöthig, A., Cokoja, M., D’Elia, V., Högerl, M. P., … Kühn, F. E. (2016). CCDC 1428063: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc1jy0k1en
dc.relation.isSupplementedByDOI:10.5517/cc1jy0k1en
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624473en
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