Mechanistic significance of the Si-O-Pd bond in the palladium-catalyzed cross-coupling reactions of alkenylsilanolates

Steven A. Tymonko, Russell C. Smith, Andrea Ambrosi, Scott E. Denmark

Research output: Contribution to journalArticle

Abstract

Through the combination of reaction kinetics (both catalytic and stoichiometric) and solid-state characterization of arylpalladium(II) alkenylsilanolate complexes, the intermediacy of covalent adducts containing Si-O-Pd linkages in the cross-coupling reactions of organosilanolates has been unambiguously established. Two mechanistically distinct pathways have been demonstrated: (1) transmetalation via a neutral 8-Si-4 intermediate that dominates in the cross-coupling of potassium alkenylsilanolates, and (2) transmetalation via an anionic 10-Si-5 intermediate that dominates in the cross-coupling of cesium alkenylsilanolates. Arylpalladium(II) alkenylsilanolate complexes bearing various phosphine ligands (both bidentate and monodentate) have been isolated, fully characterized, and evaluated for their kinetic competence under thermal (stoichiometric) and anionic (catalytic) conditions. Comparison of the rates for thermal and anionic activation demonstrates that intermediates containing the Si-O-Pd linkage are involved in the cross-coupling process.

Original languageEnglish (US)
Pages (from-to)6192-6199
Number of pages8
JournalJournal of the American Chemical Society
Volume137
Issue number19
DOIs
StatePublished - May 20 2015

ASJC Scopus subject areas

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

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