Mechanism of silver-mediated di-tert-butylsilylene transfer from a silacyclopropane to an alkene

Tom G. Driver, Keith Woerpel

Research output: Contribution to journalArticle

Abstract

Kinetic studies of the reactions of cyclohexene silacyclopropane 1 and monosubstituted alkenes in the presence of 5 mol % of (Ph3P) 2AgOTf suggested a possible mechanism for silver-mediated di-tert-butylsilylene transfer. The kinetic order in cyclohexene silacyclopropane 1 was determined to be one. Inverse kinetic saturation behavior (rate inhibition) was observed in monosubstituted alkene and cyclohexene concentrations. Saturation kinetic behavior in catalyst concentration was observed. A reactive intermediate, a silyisilver complex, was observed using low temperature 29Si NMR spectroscopy. Competition experiments between substituted styrenes and a deficient amount of 1 correlated well with the Hammett equation and provided a p value of -0.62 ± 0.02 using σp constants. These data support a mechanism involving reversible silver-promoted di-tert-butylsilylene extrusion from 1 followed by irreversible concerted electrophilic attack of the silylsilver intermediate on the alkene.

Original languageEnglish (US)
Pages (from-to)9993-10002
Number of pages10
JournalJournal of the American Chemical Society
Volume126
Issue number32
DOIs
StatePublished - Aug 18 2004

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Alkenes
Silver
Olefins
Kinetics
Styrenes
Nuclear magnetic resonance spectroscopy
Extrusion
Styrene
Magnetic Resonance Spectroscopy
Catalysts
Temperature
di-tert-butylsilylene
cyclohexene
Experiments

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Mechanism of silver-mediated di-tert-butylsilylene transfer from a silacyclopropane to an alkene. / Driver, Tom G.; Woerpel, Keith.

In: Journal of the American Chemical Society, Vol. 126, No. 32, 18.08.2004, p. 9993-10002.

Research output: Contribution to journalArticle

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