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Proton- and Reductant-Assisted Dioxygen Activation by a Nonheme Iron(II) Complex to Form an Oxoiron(IV) Intermediate

Authors

  • Aurore Thibon Dr.,

    1. Institut de Chimie Moléculaire et des Matériaux d'Orsay, UMR CNRS 8182, Laboratoire de Chimie Inorganique, Université Paris Sud 11, 91405 Orsay Cedex (France), Fax: (+33) 1-6915-4754
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  • Jason England Dr.,

    1. Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, 207 Pleasant St. SE, Minneapolis, MN 55455 (USA), Fax: (+1) 612-624-7029
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  • Marlène Martinho Dr.,

    1. Department of Chemistry, Carnegie Mellon University, Pittsburgh, PA 15213 (USA)
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  • Victor G. Young Jr. Dr.,

    1. Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, 207 Pleasant St. SE, Minneapolis, MN 55455 (USA), Fax: (+1) 612-624-7029
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  • Jonathan R. Frisch,

    1. Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, 207 Pleasant St. SE, Minneapolis, MN 55455 (USA), Fax: (+1) 612-624-7029
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  • Régis Guillot Dr.,

    1. Institut de Chimie Moléculaire et des Matériaux d'Orsay, UMR CNRS 8182, Laboratoire de Chimie Inorganique, Université Paris Sud 11, 91405 Orsay Cedex (France), Fax: (+33) 1-6915-4754
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  • Jean-Jacques Girerd Prof. Dr.,

    1. Institut de Chimie Moléculaire et des Matériaux d'Orsay, UMR CNRS 8182, Laboratoire de Chimie Inorganique, Université Paris Sud 11, 91405 Orsay Cedex (France), Fax: (+33) 1-6915-4754
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  • Eckard Münck Prof. Dr.,

    1. Department of Chemistry, Carnegie Mellon University, Pittsburgh, PA 15213 (USA)
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  • Lawrence Que Jr. Prof. Dr.,

    1. Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, 207 Pleasant St. SE, Minneapolis, MN 55455 (USA), Fax: (+1) 612-624-7029
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  • Frédéric Banse Dr.

    1. Institut de Chimie Moléculaire et des Matériaux d'Orsay, UMR CNRS 8182, Laboratoire de Chimie Inorganique, Université Paris Sud 11, 91405 Orsay Cedex (France), Fax: (+33) 1-6915-4754
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  • This work is the result of equal efforts from A.T. and J.E. It was supported by the U.S. National Institutes of Health (GM-33162 to L.Q. and EB-001475 to E.M.) and by the French program “Energie, Conception Durable 2004” (ACI BioCatOx ECD009 to F.B.). Data collection for the X-ray structure of 3(OTf)2 was performed at ChemMatCARS Sector 15, which is principally supported by the National Science Foundation/Department of Energy under grant number CHE-0535644. Use of the Advanced Photon Source was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357.

Abstract

original image

With a little help from some friends: With the aid of HClO4 as proton and BPh4 as electron source, the Fe complex of a pentadentate pyridyl-appended cyclam ligand can activate dioxygen to yield the corresponding oxoiron(IV) complex (see scheme; TMC-py=1-(2′-pyridylmethyl)-4,8,11-trimethyl-1,4,8,11-tetraazacyclotetradecane; C gray, Fe magenta, N blue, O red). This transformation is proposed to occur via a hydroperoxoiron(III) intermediate.

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