A Model of the [FeFe] Hydrogenase Active Site with a Biologically Relevant Azadithiolate Bridge: A Spectroscopic and Theoretical Investigation

Authors

  • Dr. Özlen F. Erdem,

    Corresponding author
    1. Max-Planck-Institut für Bioanorganische Chemie, Stiftstrasse 34-36, 45470 Mülheim an der Ruhr (Germany), Fax: (+49) 208-306-3955
    • Max-Planck-Institut für Bioanorganische Chemie, Stiftstrasse 34-36, 45470 Mülheim an der Ruhr (Germany), Fax: (+49) 208-306-3955
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  • Dr. Lennart Schwartz,

    1. Department of Photochemistry and Molecular Science, Uppsala University, Box 523, 75120 Uppsala (Sweden)
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  • Dr. Matthias Stein,

    1. Max-Planck-Institut für Dynamik komplexer technischer Systeme, Sandtorstrasse 1, 39106 Magdeburg (Germany)
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  • Dr. Alexey Silakov,

    1. Max-Planck-Institut für Bioanorganische Chemie, Stiftstrasse 34-36, 45470 Mülheim an der Ruhr (Germany), Fax: (+49) 208-306-3955
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  • Dr. Sandeep Kaur-Ghumaan,

    1. Department of Photochemistry and Molecular Science, Uppsala University, Box 523, 75120 Uppsala (Sweden)
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  • Dr. Ping Huang,

    1. Department of Photochemistry and Molecular Science, Uppsala University, Box 523, 75120 Uppsala (Sweden)
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  • Dr. Sascha Ott,

    Corresponding author
    1. Department of Photochemistry and Molecular Science, Uppsala University, Box 523, 75120 Uppsala (Sweden)
    • Department of Photochemistry and Molecular Science, Uppsala University, Box 523, 75120 Uppsala (Sweden)
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  • Dr. Edward J. Reijerse,

    1. Max-Planck-Institut für Bioanorganische Chemie, Stiftstrasse 34-36, 45470 Mülheim an der Ruhr (Germany), Fax: (+49) 208-306-3955
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  • Prof. Dr. Wolfgang Lubitz

    Corresponding author
    1. Max-Planck-Institut für Bioanorganische Chemie, Stiftstrasse 34-36, 45470 Mülheim an der Ruhr (Germany), Fax: (+49) 208-306-3955
    • Max-Planck-Institut für Bioanorganische Chemie, Stiftstrasse 34-36, 45470 Mülheim an der Ruhr (Germany), Fax: (+49) 208-306-3955
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  • Gudrun Klihm is gratefully acknowledged for her technical support in the EPR experiments. Financial support from the Max Planck Society, the Swedish Research Council (S.O.), the Wenner Gren Foundation (S.K.-G.), the Swedish Energy Agency, the Knut and Alice Wallenberg Foundation, the Klaus Tschira Foundation (M.S.), and the EU (FP7 Energy 212508 “SOLAR-H2”) is gratefully acknowledged.

Abstract

original image

Convincing evidence for the presence of a nitrogen atom in the dithiolate bridge of the active site of native [FeFe] hydrogenases (B) is provided by a spectroscopic, electrochemical, and theoretical study of a well-characterized structural mimic of the [FeFe] hydrogenase subcluster (picture: 14N matched-HYSCORE spectrum of the model compound A). This result should help to understand the mechanism of dihydrogen conversion and production.

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