Nonheme Iron Centers in Oxygen Activation: Characterization of an Iron(III) Hydroperoxide Intermediate

Authors

  • Dr. Marcel Lubben,

    1. Department of Organic and Molecular Inorganic Chemistry, Groningen Center for Catalysis and Synthesis, University of Groningen, Nijenborgh 4, NL-9747 AG Groningen (The Netherlands)
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  • Dr. Auke Meetsma,

    1. Department of Organic and Molecular Inorganic Chemistry, Groningen Center for Catalysis and Synthesis, University of Groningen, Nijenborgh 4, NL-9747 AG Groningen (The Netherlands)
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  • Elizabeth C. Wilkinson,

    1. Department of Chemistry, University of Minnesota, Minneapolis, MN 55455 (USA). Telefax: Int. code + (612)624-7029
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  • Prof. Ben Feringa,

    Corresponding author
    1. Department of Organic and Molecular Inorganic Chemistry, Groningen Center for Catalysis and Synthesis, University of Groningen, Nijenborgh 4, NL-9747 AG Groningen (The Netherlands)
    • Department of Organic and Molecular Inorganic Chemistry, Groningen Center for Catalysis and Synthesis, University of Groningen, Nijenborgh 4, NL-9747 AG Groningen (The Netherlands)
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  • Prof. Lawrence Que Jr.

    Corresponding author
    1. Department of Chemistry, University of Minnesota, Minneapolis, MN 55455 (USA). Telefax: Int. code + (612)624-7029
    • Department of Chemistry, University of Minnesota, Minneapolis, MN 55455 (USA). Telefax: Int. code + (612)624-7029
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  • Financial support of this research by Unilever Research (Vlaardingen, Netherlands) to B. L. F. and the National Institutes of Health (USA) to L. Q. (GM-33162) is gratefully acknowledged. E. C. W. thanks the NIH for a predoctoral traineeship (GM-07323).

Abstract

original image

A new pentadentate nitrogen ligand facilitates the synthesis of a low-spin iron(II) complex, which reacts with H2O2 at low temperature to form the transient purple complex 1. Complex 1 was formulated as an FeIIIOOH complex, the first synthetic example of such a species to be characterized by electrospray ionization mass spectrometry. Furthermore, 1 oxidizes cyclohexane efficiently, thus supporting the notion that an FeIIIOOH moiety can participate in oxygen activation mechanisms of nonheme iron enzymes.

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