Dioxygen Binding at Ambient Temperature: Formation of a Novel Peroxodicopper(II) Complex with an Azole Macrocyclic Ligand

Authors

  • Dr. Johan E. Bol,

    1. Leiden Institute of Chemistry, Gorlaeus Laboratories, Leiden University, P.O. Box 9502, 2300 RA Leiden (The Netherlands), Fax: Int. code +(71)527-4451, e-mail: reedijk.univ.nl
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  • Dr. Willem L. Driessen,

    Corresponding author
    1. Leiden Institute of Chemistry, Gorlaeus Laboratories, Leiden University, P.O. Box 9502, 2300 RA Leiden (The Netherlands), Fax: Int. code +(71)527-4451, e-mail: reedijk.univ.nl
    • Leiden Institute of Chemistry, Gorlaeus Laboratories, Leiden University, P.O. Box 9502, 2300 RA Leiden (The Netherlands), Fax: Int. code +(71)527-4451, e-mail: reedijk.univ.nl
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  • Dr. Raymond Y. N. Ho,

    1. Leiden Institute of Chemistry, Gorlaeus Laboratories, Leiden University, P.O. Box 9502, 2300 RA Leiden (The Netherlands), Fax: Int. code +(71)527-4451, e-mail: reedijk.univ.nl
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  • Bas Maase,

    1. Leiden Institute of Chemistry, Gorlaeus Laboratories, Leiden University, P.O. Box 9502, 2300 RA Leiden (The Netherlands), Fax: Int. code +(71)527-4451, e-mail: reedijk.univ.nl
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  • Prof. Dr. Lawrence Que Jr.,

    Corresponding author
    1. Department of Chemistry, University of Minnesota, 207 Pleasant Street SE, Minneapolis MN 55455 (USA), Fax: Int. code +612-624-7029, e-mail: que@chem.sun.chem.umn.edu
    • Department of Chemistry, University of Minnesota, 207 Pleasant Street SE, Minneapolis MN 55455 (USA), Fax: Int. code +612-624-7029, e-mail: que@chem.sun.chem.umn.edu
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  • Prof. Dr. Jan Reedijk

    Corresponding author
    1. Leiden Institute of Chemistry, Gorlaeus Laboratories, Leiden University, P.O. Box 9502, 2300 RA Leiden (The Netherlands), Fax: Int. code +(71)527-4451, e-mail: reedijk.univ.nl
    • Leiden Institute of Chemistry, Gorlaeus Laboratories, Leiden University, P.O. Box 9502, 2300 RA Leiden (The Netherlands), Fax: Int. code +(71)527-4451, e-mail: reedijk.univ.nl
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  • This work was performed under the auspices of the Holland Research School of Molecular Chemistry (HRMSC). The research in Minnesota was supported by the US National Institute of Health (grant no. GM-33162 and fellowship no. GM-17849). We are grateful to Prof. Dr. A. D. Zuberbühler (Universität Basel, Switzerland) for fruitful discussions.

Abstract

original image

The protective pocket of hemocyanin is mimicked by the novel macrocyclic ligand MEPY22PZ (see schematic drawing on the right), which was used to make a Cu2[BOND]O2 adduct. Proper design of a ligand with azole donors connected by ethylene spacers illustrates how metal–O2 adducts can be stabilized at ambient temperatures and in protic solvents. The purple trans-μ-1,2-CuII-O2-CuII species was obtained by oxygenation of the parent CuI compound and by addition of H2O2 and base to the dinuclear CuII complex.

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