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“Aurophilicity” as a Consequence of Relativistic Effects: The Hexakis(triphenylphosphaneaurio)methane Dication [(Ph3PAu)6C]2⊕

Authors

  • Dipl.-Chem. Franz Scherbaum,

    1. Anorganisch-chemisches Institut der Technischen Universität München, Lichtenbergstrasse 4, D-8046 Garching (FRG)
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  • Andreas Grohmann,

    1. Anorganisch-chemisches Institut der Technischen Universität München, Lichtenbergstrasse 4, D-8046 Garching (FRG)
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  • Dipl.-Chem. Brigitte Huber,

    1. Anorganisch-chemisches Institut der Technischen Universität München, Lichtenbergstrasse 4, D-8046 Garching (FRG)
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  • Prof. Dr. Carl Krüger,

    1. Anorganisch-chemisches Institut der Technischen Universität München, Lichtenbergstrasse 4, D-8046 Garching (FRG)
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    • Guest professor from the Max-Planck-Institut für Kohlenforschung, Mülheim a. d. Ruhr (FRG)

  • Prof. Dr. Hubert Schmidbaur

    Corresponding author
    1. Anorganisch-chemisches Institut der Technischen Universität München, Lichtenbergstrasse 4, D-8046 Garching (FRG)
    • Anorganisch-chemisches Institut der Technischen Universität München Lichtenbergstrasse 4, D-8046 Garching (FRG)
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  • This work was supported by the Deutsche Forschungsgemeinschaft (Leibniz program), the Fonds der Chemischen Industrie, and Degussa AG, Hanau. We thank J. Riede for measurement of the crystallographic data set and Finnigan MAT for the FAB-MS measurements.

Abstract

original image

The class of “porcupine compounds”, includes the title cation 1, whose structure has been determined as the BPh4 salt. The analytically, mass-spectrometrically and crystallographically detected interstitial C atom occupies the crystallographic inversion center in an octahedron composed of gold atoms: the structure is probably stabilized by AuċAu interactions. The periphery of tetraauriomethanes is apparently “aurophile” with respect to further LAu ions, so that the hypervalent complex cation [C(AuL)6]2⊕ is formed spontaneously. The supposedly uncentered octahedral cluster cations formulated previously as (AuL)math image were in fact probably indentical with the C-centered species described here.

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