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

Chul Ho Jun; Robert H. Crabtree

doi:10.1016/0022-328X(93)80236-5

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

Chul Ho Jun, Robert H. Crabtree

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

162 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 language	English
Pages (from-to)	177-187
Number of pages	11
Journal	Journal of Organometallic Chemistry
Volume	447
Issue number	2
DOIs	https://doi.org/10.1016/0022-328X(93)80236-5
Publication status	Published - 1993 Apr 6

Bibliographical note

Funding 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

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

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10.1016/0022-328X(93)80236-5

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

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).",

author = "Jun, {Chul Ho} and Crabtree, {Robert H.}",

note = "Funding 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.",

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doi = "10.1016/0022-328X(93)80236-5",

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AU - Jun, Chul Ho

AU - Crabtree, Robert H.

N1 - Funding 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.

PY - 1993/4/6

Y1 - 1993/4/6

N2 - 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).

AB - 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

Abstract

Bibliographical note

All Science Journal Classification (ASJC) codes

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