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

Markus R. Anneser, Stefan Haslinger, Alexander Pöthig, Mirza Cokoja, Valerio D’Elia, Manuel Peter Hogerl, Jean-Marie Basset, Fritz E. Kühn

Research output: Contribution to journalArticlepeer-review

47 Scopus citations

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.
Original languageEnglish (US)
Pages (from-to)6449-6455
Number of pages7
JournalDalton Trans.
Volume45
Issue number15
DOIs
StatePublished - 2016

Bibliographical note

KAUST Repository Item: Exported on 2020-10-01
Acknowledgements: 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).

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