Dehydrogenative silation, isomerization and the control of syn- vs. anti-addition in the hydrosilation of alkynes

Chul-Ho Jun, Robert H. Crabtree

Research output: Contribution to journalArticle

132 Citations (Scopus)

Abstract

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).

Original languageEnglish
Pages (from-to)177-187
Number of pages11
JournalJournal of Organometallic Chemistry
Volume447
Issue number2
DOIs
Publication statusPublished - 1993 Apr 6

Fingerprint

Alkynes
alkynes
Isomerization
isomerization
Catalysts
Iridium
products
Silanes
Isomers
catalysts
iridium
silanes
elimination
isolation
isomers
vinylsilane
chlorotris(triphenylphosphine)rhodium

All Science Journal Classification (ASJC) codes

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

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abstract = "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).",
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Dehydrogenative silation, isomerization and the control of syn- vs. anti-addition in the hydrosilation of alkynes. / Jun, Chul-Ho; Crabtree, Robert H.

In: Journal of Organometallic Chemistry, Vol. 447, No. 2, 06.04.1993, p. 177-187.

Research output: Contribution to journalArticle

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