Mechanistic duality in palladium-catalyzed cross-coupling reactions of aryldimethylsilanolates. Intermediacy of an 8-Si-4 arylpalladium(II) silanolate

Scott E. Denmark, Russell C. Smith

Research output: Contribution to journalArticle

Abstract

(Chemical Equation Presented) The mechanism of palladium-catalyzed cross-coupling reactions of potassium (4-methoxyphenyl)dimethyl silanolate has been investigated. Under catalysis by (t-Bu3P)2Pd, the coupling with 1-bromo-4-fluorobenzene displays the following rate equation: rate = kobs[R3SiOK]0[ArylBr]0, with kobs = k[(t-Bu3P)2Pd]0.98. An independent study of the individual steps of the catalytic cycle has revealed a dual mechanistic pathway. The transmetalation can occur by a thermal process via an 8-Si-4 intermediate without the need for anionic activation. Additionally, arylsilanolates can serve as activators for transmetalation via a hypervalent 10-Si-5 siliconate intermediate.

Original languageEnglish (US)
Pages (from-to)1243-1245
Number of pages3
JournalJournal of the American Chemical Society
Volume132
Issue number4
DOIs
StatePublished - Feb 3 2010

ASJC Scopus subject areas

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

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