An unusual, highly selective C-Si coupling reaction takes place upon treating the platinum(II) alkyl complex cis-(DIPPIDH)(DIPPID)PtMe (2) (DIPPIDH = α2-(diisopropyl-phosphino)isodurene, 1) with HSiR3 (R3 = Et3, EtMe2, Me2Ph), leading to formation of MeSiR3 and the hydrido complex trans-(DIPPIDH)(DIPPID)PtH (5). The overall process involves activation of a Si-H bond, reverse-cyclometalation of the phosphine ligand DIPPIDH (1), and C-Si elimination. The resulting thermally stable platinum(II) hydride complex 5 was independently prepared by thermolysis of a platinum(II) dihydride, trans-(DIPPIDH)2PtH2 (6), which was obtained by reaction of 2 with H2. In the absence of silane, the cis complex 2 isomerizes thermally to trans-(DIPPIDH)(DIPPID)PtMe (3), which does not react productively with silanes. Our results indicate that opening of the metallacycle of 2 by benzylic C-H formation is kinetically preferred over formation of CH4 or CH3SiR3.
|Number of pages||4|
|Publication status||Published - Sep 14 1998|
ASJC Scopus subject areas
- Inorganic Chemistry
- Organic Chemistry