A Silica-Supported Monoalkylated Tungsten Dioxo Complex Catalyst for Olefin Metathesis

Niladri Maity, Samir Barman, Yury Minenkov, Samy Ould-Chikh, Edy Abou-Hamad, Tao Ma, Ziyauddin S. Qureshi, Luigi Cavallo, Valerio D'Elia*, Bruce C. Gates, Jean Marie Basset

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

43 Scopus citations

Abstract

A well-defined silica-supported monoalkylated tungsten dioxo complex [(Si-O-)W(=O)2(CH2-tBu)] was prepared by treatment of highly dehydroxylated silica (SiO2-700: silica treated at 700 °C under high vacuum) with an ionic precursor complex [NEt4][W(=O)3(CH2-tBu)]. The identity of the resulting neutral monoalkylated tungsten dioxo surface complex was established by means of elemental microanalysis and spectroscopic studies (IR, solid-state NMR, Raman, and X-ray absorption spectroscopies). The supported tungsten complex was found to act as a precatalyst for the self-metathesis of 1-octene in a batch reactor. The mechanistic implications of this reaction are discussed with the support of DFT calculations highlighting the potential occurrence of thus-far unexplored mechanistic pathways.

Original languageEnglish (US)
Pages (from-to)2715-2729
Number of pages15
JournalACS Catalysis
Volume8
Issue number4
DOIs
StatePublished - Apr 6 2018

Keywords

  • Olefin metathesis
  • mechanistic study
  • metallacyclobutane intermediate
  • tungsten alkylidene
  • tungsten dioxo complex

ASJC Scopus subject areas

  • General Chemistry
  • Catalysis

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