Regular paper
Hydrosilylation of phenylacetylene catalyzed by [Ir(COD)(η2-iPr2PCH2CH2OMe)][BF4]

https://doi.org/10.1016/0022-328X(94)05110-WGet rights and content

Abstract

In the presence of the complexes [Ir(diolefin)(η2-iPr2PCH2CH2NMe2)][BF4] (diolefin = 1,5-cyclooctadiene (COD) (1) or tetrafluorobenzobarrelene (TFB) (2)) and [Ir(diolefin)(η2-iPr2PCH2CH2OMe)][BF4] (diolefin = COD (3) or TFB (4)), phenylacetylene undergoes reaction with triethylsilane. In all experiments carried out PhCHCH2, PhCCSiEt3, cis-PhCHCH(SiEt3), trans-PhCHCH(SiEt3) and Ph(SiEt3)CCH2 were obtained. An investigation in detail for the catalyst 3 suggests that, under catalytic conditions, the complexes [IrH(C2Ph)(COD)(η2-iPr2PCH2CH2OMe)]BF4 (5) and [IrH(SiEt3)(COD)(η2-iPr2PCH2CH2OMe)]BF4 (6) are formed. Complex 5 is the key intermediate for the formation of PhCCSiEt3, while 6 is the species leading to cis-PhCHCH(SiEt3). The isomer trans-PhChCH(SiEt)3) is formed by isomerization of cis-PhCHCH(SiEt3). The mechanisms of formation of these compounds are discussed.

References (30)

  • B. Marciniec et al.

    J. Organomet. Chem.

    (1993)
  • I. Ojima et al.

    J. Organomet. Chem.

    (1974)
  • M.F. Lappert et al.

    J. Organomet. Chem.

    (1984)
  • H.M. Dickers et al.

    J. Organomet. Chem.

    (1978)
  • K.A. Brady et al.

    J. Organomet. Chem.

    (1981)
  • C.H. Jun et al.

    J. Organomet. Chem.

    (1993)
  • M.J. Fernández et al.

    J. Mol. Catal.

    (1988)
  • H. Watanabe et al.

    J. Organomet. Chem.

    (1977)
  • J.E. Hill et al.

    J. Organomet. Chem.

    (1977)
  • M.F. Lappert et al.

    J. Organomet. Chem.

    (1984)
  • M. Brockmann et al.

    J. Organomet. Chem.

    (1986)
  • B. Marciniec et al.
  • I. Ojima
  • I. Ojima et al.

    Organometallics

    (1990)
  • M.A. Esteruelas et al.

    Organometallics

    (1993)
  • Cited by (0)

    View full text