Dinuclear Palladium and Platinum Complexes with Bridging Silylene Ligands. Preparation Using (Aminosilyl)boronic Ester as the Ligand Precursor and Their Reactions with Alkynes

DOI Web Site Research Data 10 Citations 113 References
  • Makoto Tanabe
    Chemical Resources Laboratory, Tokyo Institute of Technology, 4259-R1-3 Nagatsuta, Midori-ku, Yokohama 226-8503, Japan
  • Jian Jiang
    Chemical Resources Laboratory, Tokyo Institute of Technology, 4259-R1-3 Nagatsuta, Midori-ku, Yokohama 226-8503, Japan
  • Hideto Yamazawa
    Chemical Resources Laboratory, Tokyo Institute of Technology, 4259-R1-3 Nagatsuta, Midori-ku, Yokohama 226-8503, Japan
  • Kohtaro Osakada
    Chemical Resources Laboratory, Tokyo Institute of Technology, 4259-R1-3 Nagatsuta, Midori-ku, Yokohama 226-8503, Japan
  • Toshimichi Ohmura
    Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510, Japan
  • Michinori Suginome
    Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510, Japan

Description

Equimolar reactions of (aminosilyl)boronic ester Et2NSiPh2BOCMe2CMe2O with zerovalent complexes of Pt and Pd, M(PMe3)4 (M = Pt, Pd), afforded the dinuclear complexes with bridging silylene ligands {M(PMe3)2}2(μ-SiPh2)2 (1: M = Pt, 2: M = Pd). X-ray crystallographic studies of 1 and 2 revealed a Si···Si interaction in the M2Si2 four-membered ring. Diplatinum complex 1 reacted with arylacetylenes HC≡CAr (Ar = C6H5, C6H4Me-4), yielding 3,5-disila-4-platinacyclopentene Pt(SiPh2CAr═CHSiPh2)(PMe3)2 (3a: Ar = C6H5, 3b: Ar = C6H4Me-4), although the reaction mixture also contained complexes with the alkyne or the alkynyl ligands. The reaction of PhC≡CPh with dipalladium complex 2 gave Pd(SiPh2CPh═CPhSiPh2)(PMe3)2 as well as alkyne complex Pd(η2-PhC≡CPh)(PMe3)2. The reactions of HC≡CAr (Ar = C6H5, C6H4Me-4) with Pt(SiHPh2)2(PMe3)2 also formed 3a and 3b accompanied by 6-sila-3-platina-1,4-cyclohexadienes Pt(CAr═CHSiPh2CH═CAr)(PMe3)2 as the byproduct. A similar reaction of HC≡CCOOMe with Pt(SiPh2H)2(PMe3)2 yielded th...

Journal

  • Organometallics

    Organometallics 30 (15), 3981-3991, 2011-07-06

    American Chemical Society (ACS)

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