Well-defined silica-supported Mo-alkylidene catalyst precursors containing one OR substituent: Methods of preparation and structure-reactivity relationship in alkene metathesis

Nuria Rendón*, Romain Berthoud, Frédéric Blanc, David Gajan, Tarun Maishal, Jean-Marie Maurice Basset, Christophe Copéret, Anne Lesage, Lyndon Emsley, Smaranda C. Marinescu, Rojendra Singh, Richard R. Schrock

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

53 Scopus citations

Abstract

The monosiloxy surface complexes [(≡SiO)Mo(≡NAr)(=CHC-Me 2R′)(OR)± (R′ = Me or Ph; OR = OtBu, OCMe(CF 3)2 or OAr) are obtained by grafting onto SiO 2-(700) either symmetric Mo-alkylidene derivatives [Mo(≡NAr)(=CHCMe2R′)(OR)2± or asymmetric derivatives, that is, with two different pendant ligands, one amido and one alkoxy/aryloxy, [Mo(≡ NAr)(=CHCMe2R′)(OR)(NC 6H8)±. The formation of these complexes was confirmed by mass-balance analysis, and infrared (IR) and NMR spectroscopies. These systems are highly efficient catalyst precursors for the metathesis of acyclic alkenes; the best results were seen when OR = OCMe-(CF3) 2. Nevertheless, they display poor performances in ring-closing metathesis, possibly due to the rigidity of the metal center (as evidenced by NMR spectroscopy), which therefore slows the rate of the metathesis.

Original languageEnglish (US)
Pages (from-to)5083-5089
Number of pages7
JournalChemistry - A European Journal
Volume15
Issue number20
DOIs
StatePublished - May 11 2009

Keywords

  • Metathesis
  • Molybdenum
  • Silica supports
  • Solid-state NMR spectroscopy
  • Surface chemistry

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Organic Chemistry

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