Alkyne hydrosilation has been examined in detail for the catalysts [IrH(H2O)(bq)L2]SbF6 (L = PPh3, bq = 7,8-benzoquinolinato) and RhCl(PPh3)3. Factors that favor the normal syn- or the unusual anti-silane addition to the alkynes are examined. Two other unusual products are noted: the dehydrogenative silation product RCCSiR3, formed by β-elimination in a vinylmetal intermediate and allylsilane products of vinylsilane isomerization. The iridium catalyst is advantageous in that it does not give fast vinylsilane isomerization, as does RhCl(PPh3)3, so allowing formation and isolation of the thermodynamically less stable cis-, rather than the more stable trans-vinylsilane isomer RCHCH(SiR'3).
Bibliographical noteFunding Information:
We thank the Korea Institute for Defense and Development for a Fellowship (C.-H.J.) and the National Science Foundation (R.H.C.) for support.
All Science Journal Classification (ASJC) codes
- Physical and Theoretical Chemistry
- Organic Chemistry
- Inorganic Chemistry
- Materials Chemistry