Pushing the σ-Donor Strength in Iridium Pincer Complexes: Bis(silylene) and Bis(germylene) Ligands Are Stronger Donors than Bis(phosphorus(III)) Ligands

Authors

  • Dr. Andreas Brück,

    1. Department of Chemistry: Metalorganics and Inorganic Materials, Technische Universität Berlin, Strasse des 17. Juni 135, Sekr. C2, 10623 Berlin (Germany)
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  • M. Sc. Daniel Gallego,

    1. Department of Chemistry: Metalorganics and Inorganic Materials, Technische Universität Berlin, Strasse des 17. Juni 135, Sekr. C2, 10623 Berlin (Germany)
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  • Dipl.-Chem. Wenyuan Wang,

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

  • Prof. Dr. Matthias Driess,

    Corresponding author
    1. Department of Chemistry: Metalorganics and Inorganic Materials, Technische Universität Berlin, Strasse des 17. Juni 135, Sekr. C2, 10623 Berlin (Germany)
    • Department of Chemistry: Metalorganics and Inorganic Materials, Technische Universität Berlin, Strasse des 17. Juni 135, Sekr. C2, 10623 Berlin (Germany)
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  • Prof. Dr. John F. Hartwig

    Corresponding author
    1. University of California, Department of Chemistry, 718 Latimer Hall, Berkeley, CA 94720 (USA)
    • University of California, Department of Chemistry, 718 Latimer Hall, Berkeley, CA 94720 (USA)
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  • Financial support by the Einstein Foundation Berlin (J.F.H.) and the Cluster of Excellence UniCat (financed by the Deutsche Forschungsgemeinschaft and administered by the TU Berlin) is gratefully acknowledged. A.B. thanks the Deutsche Forschungsgemeinschaft for an initial postdoctoral fellowship to work with J.F.H. (BR 4069/1-1). We thank Dr. S. Krackl for help with X-ray crystal structures.

Abstract

original image

Breaking the donor limits: The remarkable coordination chemistry of ECHE (E=Si, Ge) ligands with Group 9 metals (Ir, Rh) and their application in catalytic C[BOND]H borylation of arenes was investigated. The spectroscopic and structural features of the first [ECE] iridium complexes show the stronger σ-donating properties of the divalent Si and Ge pincer ligands compared to analogous PIII-based ligands.

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