Synthesis of an oxo trialkyl tungsten fluoride complex and its dual reactivity with silica dehydroxylated at high temperature

Nicolas Merle, Etienne Mazoyer, Kai C. Szeto, Pascal Rouge, Aimery de Mallmann, Elise Berrier, Laurent Delevoye, Régis M. Gauvin, Christopher P. Nicholas*, Jean Marie Basset, Mostafa Taoufik

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

1 Scopus citations

Abstract

The novel complex W (=O)Np3F has been prepared by fluorination of the corresponding chloride counterpart with AgBF4. The reactivity of this complex with silica dehydroxylated at 700 °C afforded a well-defined silica supported monopodal tungsten oxo trialkyl surface species (≡SiO)W (=O)Np3. The reaction proceeds both through silanolysis of the W-F bond and opening of a siloxane bridge, with formation of a Si-F fragment, thanks to the affinity of silicon for fluoride. The resulting surface species was characterized by elemental analysis, DRIFT, solid state NMR and EXAFS spectroscopy. This material presenting fluorine on its surface shows an enhanced catalytic activity in propylene self-metathesis compared to its monopodal counterpart (≡SiO)W (=O)Np3 (prepared from W (=O)Np3Cl) suggesting that the Si-F in a close vicinity to the W decreases the electron density of the W and thus increases its reactivity towards the olefinic substrate.

Original languageEnglish (US)
Pages (from-to)11-17
Number of pages7
JournalJournal of Organometallic Chemistry
Volume869
DOIs
StatePublished - Aug 15 2018

Keywords

  • Catalysis
  • Fluorine ligand
  • Olefin metathesis
  • Oxo ligand
  • Surface chemistry
  • Tungsten

ASJC Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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