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

39 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

Bibliographical note

Funding Information:
V.D.E. thanks the Thailand Research Fund (Grant No. RSA6080059) for funding. Notes The authors declare no competing financial interest.

Funding Information:
The research was supported by the King Abdullah University of Science and Technology (KAUST). The authors acknowledge Dr. Christian G. Canlas and Erjia Guan for their assistance. The work at the University of California was supported by the U.S. Department of Energy (DOE, Basic Energy Sciences DE-FG02-04ER15513). We acknowledge the European Synchrotron Radiation Facility for provision of synchrotron radiation facilities, and we would like to thank Antonio Aguilar for assistance in using beamline BM30 B.

Publisher Copyright:
© 2018 American Chemical Society.

Keywords

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

ASJC Scopus subject areas

  • General Chemistry
  • Catalysis

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