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Issue 15, 2016
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Binding of molecular oxygen by an artificial heme analogue: investigation on the formation of an Fe–tetracarbene superoxo complex

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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.

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

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Publication details

The article was received on 06 Feb 2016, accepted on 26 Feb 2016 and first published on 26 Feb 2016


Article type: Paper
DOI: 10.1039/C6DT00538A
Citation: Dalton Trans., 2016,45, 6449-6455
  • Open access: Creative Commons BY-NC license
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    Binding of molecular oxygen by an artificial heme analogue: investigation on the formation of an Fe–tetracarbene superoxo complex

    M. R. Anneser, S. Haslinger, A. Pöthig, M. Cokoja, V. D'Elia, M. P. Högerl, J. Basset and F. E. Kühn, Dalton Trans., 2016, 45, 6449
    DOI: 10.1039/C6DT00538A

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