Bis(imino)pyridine cobalt-catalyzed dehydrogenative silylation of alkenes: Scope, mechanism, and origins of selective allylsilane formation

Crisita Carmen Hojilla Atienza, Tianning Diao, Keith J. Weller, Susan A. Nye, Kenrick M. Lewis, Johannes G P Delis, Julie L. Boyer, Aroop K. Roy, Paul J. Chirik

Research output: Contribution to journalArticle

Abstract

The aryl-substituted bis(imino)pyridine cobalt methyl complex, ( MesPDI)CoCH3 (MesPDI = 2,6-(2,4,6-Me 3C6H2-N=CMe)2C5H 3N), promotes the catalytic dehydrogenative silylation of linear α-olefins to selectively form the corresponding allylsilanes with commercially relevant tertiary silanes such as (Me3SiO) 2MeSiH and (EtO)3SiH. Dehydrogenative silylation of internal olefins such as cis- and trans-4-octene also exclusively produces the allylsilane with the silicon located at the terminus of the hydrocarbon chain, resulting in a highly selective base-metal-catalyzed method for the remote functionalization of C-H bonds with retention of unsaturation. The cobalt-catalyzed reactions also enable inexpensive α-olefins to serve as functional equivalents of the more valuable α, ω-dienes and offer a unique method for the cross-linking of silicone fluids with well-defined carbon spacers. Stoichiometric experiments and deuterium labeling studies support activation of the cobalt alkyl precursor to form a putative cobalt silyl, which undergoes 2,1-insertion of the alkene followed by selective β-hydrogen elimination from the carbon distal from the large tertiary silyl group and accounts for the observed selectivity for allylsilane formation.

Original languageEnglish (US)
Pages (from-to)12108-12118
Number of pages11
JournalJournal of the American Chemical Society
Volume136
Issue number34
DOIs
StatePublished - 2014

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Alkenes
Cobalt
Pyridine
Olefins
Carbon
Silanes
Deuterium
Silicon
Silicones
Hydrocarbons
Labeling
Hydrogen
Metals
Chemical activation
Fluids
allylsilane
pyridine
Experiments

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Bis(imino)pyridine cobalt-catalyzed dehydrogenative silylation of alkenes : Scope, mechanism, and origins of selective allylsilane formation. / Atienza, Crisita Carmen Hojilla; Diao, Tianning; Weller, Keith J.; Nye, Susan A.; Lewis, Kenrick M.; Delis, Johannes G P; Boyer, Julie L.; Roy, Aroop K.; Chirik, Paul J.

In: Journal of the American Chemical Society, Vol. 136, No. 34, 2014, p. 12108-12118.

Research output: Contribution to journalArticle

Atienza, Crisita Carmen Hojilla ; Diao, Tianning ; Weller, Keith J. ; Nye, Susan A. ; Lewis, Kenrick M. ; Delis, Johannes G P ; Boyer, Julie L. ; Roy, Aroop K. ; Chirik, Paul J. / Bis(imino)pyridine cobalt-catalyzed dehydrogenative silylation of alkenes : Scope, mechanism, and origins of selective allylsilane formation. In: Journal of the American Chemical Society. 2014 ; Vol. 136, No. 34. pp. 12108-12118.
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abstract = "The aryl-substituted bis(imino)pyridine cobalt methyl complex, ( MesPDI)CoCH3 (MesPDI = 2,6-(2,4,6-Me 3C6H2-N=CMe)2C5H 3N), promotes the catalytic dehydrogenative silylation of linear α-olefins to selectively form the corresponding allylsilanes with commercially relevant tertiary silanes such as (Me3SiO) 2MeSiH and (EtO)3SiH. Dehydrogenative silylation of internal olefins such as cis- and trans-4-octene also exclusively produces the allylsilane with the silicon located at the terminus of the hydrocarbon chain, resulting in a highly selective base-metal-catalyzed method for the remote functionalization of C-H bonds with retention of unsaturation. The cobalt-catalyzed reactions also enable inexpensive α-olefins to serve as functional equivalents of the more valuable α, ω-dienes and offer a unique method for the cross-linking of silicone fluids with well-defined carbon spacers. Stoichiometric experiments and deuterium labeling studies support activation of the cobalt alkyl precursor to form a putative cobalt silyl, which undergoes 2,1-insertion of the alkene followed by selective β-hydrogen elimination from the carbon distal from the large tertiary silyl group and accounts for the observed selectivity for allylsilane formation.",
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AU - Atienza, Crisita Carmen Hojilla

AU - Diao, Tianning

AU - Weller, Keith J.

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