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Reactions of a Copper(II) Superoxo Complex Lead to C[BOND]H and O[BOND]H Substrate Oxygenation: Modeling Copper-Monooxygenase C[BOND]H Hydroxylation

Authors

  • Debabrata Maiti,

    1. Department of Chemistry, The Johns Hopkins University, Baltimore, MD 21218, USA, Fax: (+1) 410-516-7044
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  • Dong-Heon Lee Prof. Dr.,

    1. Department of Chemistry, The Johns Hopkins University, Baltimore, MD 21218, USA, Fax: (+1) 410-516-7044
    2. Current addresses: Department of Chemistry and Research Institute of Physics and Chemistry (RINPAC), Chonbuk National University, Jeonju 561-756, Korea
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  • Katya Gaoutchenova Dr.,

    1. Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Strasse, 35032 Marburg, Germany
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  • Christian Würtele,

    1. Institut für Anorganische und Analytische Chemie, Justus-Liebig-Universität Gießen, Heinrich-Buff-Ring 58, 35392 Gießen, Germany
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  • Max C. Holthausen Prof. Dr.,

    1. Institut für Anorganische und Analytische Chemie, Johann Wolfgang Goethe-Universität Frankfurt, Max-von-Laue Strasse 7, 60438 Frankfurt am Main, Germany
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  • Amy A. Narducci Sarjeant Dr.,

    1. Department of Chemistry, The Johns Hopkins University, Baltimore, MD 21218, USA, Fax: (+1) 410-516-7044
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  • Jörg Sundermeyer Prof. Dr.,

    1. Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Strasse, 35032 Marburg, Germany
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  • Siegfried Schindler Prof. Dr.,

    1. Institut für Anorganische und Analytische Chemie, Justus-Liebig-Universität Gießen, Heinrich-Buff-Ring 58, 35392 Gießen, Germany
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  • Kenneth D. Karlin Prof.

    1. Department of Chemistry, The Johns Hopkins University, Baltimore, MD 21218, USA, Fax: (+1) 410-516-7044
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  • We are grateful to the NIH (K.D.K., GM28962) and Deutsche Forschungsgemeinschaft (J.S., S.S., and M.C.H.) for research support.

Abstract

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Donor makes the difference: The mononuclear η1-superoxo copper(II) complex 1 undergoes dioxygen activation with the addition of hydrogen-atom donors. Net O2-derived O-atom insertion into the N-methyl group of the ligand leads to formation of a copper(II)-alkoxide product 2. The cupric superoxo species 1 itself is not capable of the observed hydroxylation reaction.

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