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A Heterobimetallic Approach To Stabilize the Elusive Disulfur Radical Trianion (“Subsulfide”) equation image

Authors

  • Dr. Shenglai Yao,

    1. Technische Universität Berlin, Department of Chemistry, Metalorganics and Inorganic Materials, Sekr. C2, Strasse des 17. Juni 135, 10623 Berlin (Germany)
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  • Dr. Peter Hrobárik,

    1. Technische Universität Berlin, Department of Chemistry: Theoretical Chemistry, Sekr. C7, Strasse des 17. Juni 135, 10623 Berlin (Germany)
    2. Institute of Inorganic Chemistry, Slovak Academy of Sciences, Dúbravská cesta 9, 84536 Bratislava (Slovakia)
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  • Dipl.-Chem. Florian Meier,

    1. Technische Universität Berlin, Department of Chemistry: Theoretical Chemistry, Sekr. C7, Strasse des 17. Juni 135, 10623 Berlin (Germany)
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  • Dipl.-Chem. Robert Rudolph,

    1. Technische Universität Berlin, Department of Chemistry, Metalorganics and Inorganic Materials, Sekr. C2, Strasse des 17. Juni 135, 10623 Berlin (Germany)
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  • Dr. Eckhard Bill,

    1. Max-Planck Institute of Chemical Energy Conversion, Stiftsstrasse 34-36, 45470 Müllheim/Ruhr (Germany)
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  • Dr. Elisabeth Irran,

    1. Technische Universität Berlin, Department of Chemistry, Metalorganics and Inorganic Materials, Sekr. C2, Strasse des 17. Juni 135, 10623 Berlin (Germany)
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  • Prof. Dr. Martin Kaupp,

    Corresponding author
    1. Technische Universität Berlin, Department of Chemistry: Theoretical Chemistry, Sekr. C7, Strasse des 17. Juni 135, 10623 Berlin (Germany)
    • Technische Universität Berlin, Department of Chemistry: Theoretical Chemistry, Sekr. C7, Strasse des 17. Juni 135, 10623 Berlin (Germany)
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  • Prof. Dr. Matthias Driess

    Corresponding author
    1. Technische Universität Berlin, Department of Chemistry, Metalorganics and Inorganic Materials, Sekr. C2, Strasse des 17. Juni 135, 10623 Berlin (Germany)
    • Technische Universität Berlin, Department of Chemistry, Metalorganics and Inorganic Materials, Sekr. C2, Strasse des 17. Juni 135, 10623 Berlin (Germany)
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Abstract

A unique heterobimetallic disulfur monoradical, complex 2, with a diamond-shaped {NiS2Pt} core has been synthesized by two-electron reduction of a supersulfido-(nacnac)nickel(II) complex (nacnac=β-diketiminato) with [Pt(Ph3P)22-C2H4)] as a platinum(0) source and isolated in 82 % yield. Strikingly, the results of DFT calculations in accordance with spectroscopic (EPR, paramagnetic NMR) and structural features of the complex revealed that the bonding situation of the S2 ligand is between the elusive “half-bonded” S2 radical trianion (equation image) and two separated S2− ligands. Accordingly, the NiII center is partially oxidized, whereas the PtII site is redox innocent. The complex can be reversibly oxidized to the corresponding Ni,Pt-disulfido monocation, compound 3, with a S[BOND]S single bond, and reacts readily with O2 to form the corresponding superoxonickel(II) and disulfidoplatinum(II) (4) complexes. These compounds have been isolated in crystalline form and fully characterized, including IR and multi-nuclear NMR spectroscopy as well as ESI mass spectrometry. The molecular structures of compounds 24 have been confirmed by single-crystal X-ray crystallography.

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