An Unusual Example of Hypervalent Silicon: A Five-Coordinate Silyl Group Bridging Two Palladium or Nickel Centers through a Nonsymmetrical Four-Center Two-Electron Bond

Authors

  • Ainara Nova,

    Corresponding author
    1. Centre for Theoretical and Computational Chemistry, Department of Chemistry, University of Oslo, P.O. Box 1033, Blindern, 0315 Oslo (Norway)
    2. Institute of Chemical Research of Catalonia (ICIQ), Avgda Països Catalans, 16, 43007 Tarragona (Spain)
    • Ainara Nova, Centre for Theoretical and Computational Chemistry, Department of Chemistry, University of Oslo, P.O. Box 1033, Blindern, 0315 Oslo (Norway)

      Nilay Hazari, The Department of Chemistry, Yale University, P.O. Box 208107, New Haven, CT 06520 (USA)

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    • These authors contributed equally.

  • Hee-Won Suh,

    1. The Department of Chemistry, Yale University, P.O. Box 208107, New Haven, CT 06520 (USA)
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    • These authors contributed equally.

  • Timothy J. Schmeier,

    1. The Department of Chemistry, Yale University, P.O. Box 208107, New Haven, CT 06520 (USA)
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  • Louise M. Guard,

    1. The Department of Chemistry, Yale University, P.O. Box 208107, New Haven, CT 06520 (USA)
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  • Odile Eisenstein,

    1. Centre for Theoretical and Computational Chemistry, Department of Chemistry, University of Oslo, P.O. Box 1033, Blindern, 0315 Oslo (Norway)
    2. Institut Charles Gerhardt, UMR 5253 CNRS-UM2, Université Montpellier 2, cc 1501, Place E. Bataillon, 34095 Montpellier (France)
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  • Nilay Hazari,

    Corresponding author
    1. The Department of Chemistry, Yale University, P.O. Box 208107, New Haven, CT 06520 (USA)
    • Ainara Nova, Centre for Theoretical and Computational Chemistry, Department of Chemistry, University of Oslo, P.O. Box 1033, Blindern, 0315 Oslo (Norway)

      Nilay Hazari, The Department of Chemistry, Yale University, P.O. Box 208107, New Haven, CT 06520 (USA)

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  • Feliu Maseras

    1. Institute of Chemical Research of Catalonia (ICIQ), Avgda Països Catalans, 16, 43007 Tarragona (Spain)
    2. Departament de Química, Universitat Autònoma de Barcelona, 08193 Bellaterra (Spain)
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  • We acknowledge support from the National Science Foundation through Grant CHE-1150826, the Research Council of Norway through a Centre of Excellence Grant (Grant No. 179568V30), the ICIQ Foundation, the Spanish MINECO (projects CTQ2011-27033, Consolider Ingenio 2010 CSD2006-0003), and the French CNRS and Ministère de l’Enseignement Supérieur et de la Recherche.

Abstract

Pd and Ni dimers supported by PSiP ligands in which two hypervalent five-coordinate Si atoms bridge the two metal centers are reported. Crystallographic characterization revealed a rare square-pyramidal geometry at Si and an unusual asymmetric M2Si2 core (M=Pd or Ni). DFT calculations showed that the unusual structure of the core is also found in a model in which the phosphine and Si centers are not part of a pincer group, thus indicating that the observed geometry is not imposed by the PSiP ligand. NBO analysis showed that an asymmetric four-center two-electron (4c-2e) bond stabilizes the hypervalent Si atoms in the M2Si2 core.

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