Primary products and mechanistic considerations in alkane metathesis

Jean Marie Basset*, Christophe Copéret, Laurent Lefort, Barry M. Maunders, Olivier Maury, Erwan Le Roux, Guillaume Saggio, Sophie Soignier, Daravong Soulivong, Glenn J. Sunley, Mostafa Taoufik, Jean Thivolle-Cazat

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

105 Scopus citations

Abstract

Alkane metathesis, a reaction catalyzed by the silica-supported tantalum hydride [(≡SiO)2Ta-H], 1, which transforms acyclic alkanes into their higher and lower homologues, was reported in 1997. New studies conducted in a continuous flow reactor in the case of propane indicate that, by varying the contact time, hydrogen and olefins are primary products. This crucial observation, as well as the known properties of tantalum alkyls to perform α-H or β-H eliminations, supports the proposition of a new mechanism involving metallacyclobutane intermediates just like in olefin metathesis. The observed selectivities for linear and branched Cn+1 and Cn+2 products as well as the linear/branched ratio can be well-explained on the basis of the minimization of steric interactions between 1,2- or 1,3-substituents in the various tantallacyclobutane intermediates or during their formation. Hydrogen plays a specific role in the cleavage of metal alkyls to complete the catalytic cycle.

Original languageEnglish (US)
Pages (from-to)8604-8605
Number of pages2
JournalJournal of the American Chemical Society
Volume127
Issue number24
DOIs
StatePublished - Jun 22 2005
Externally publishedYes

ASJC Scopus subject areas

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

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