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

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  • 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

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説明

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...

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  • Organometallics

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

    American Chemical Society (ACS)

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