WMe6 tamed by silica: ≡Si-O-WMe5 as an efficient, well-defined species for alkane metathesis, leading to the observation of a supported W-methyl/methylidyne species

Manoja K Samantaray; Emmanuel Callens; Edy Abou-Hamad; Aaron J Rossini; Cory M Widdifield; Raju Dey; Lyndon Emsley; Jean-Marie Basset

doi:10.1021/ja410747g

WMe6 tamed by silica: ≡Si-O-WMe5 as an efficient, well-defined species for alkane metathesis, leading to the observation of a supported W-methyl/methylidyne species

J Am Chem Soc. 2014 Jan 22;136(3):1054-61. doi: 10.1021/ja410747g. Epub 2014 Jan 10.

Authors

Manoja K Samantaray¹, Emmanuel Callens, Edy Abou-Hamad, Aaron J Rossini, Cory M Widdifield, Raju Dey, Lyndon Emsley, Jean-Marie Basset

Affiliation

¹ KAUST Catalysis Center (KCC), King Abdullah University of Science & Technology , 23955-6900 Thuwal, Saudi Arabia.

PMID: 24369727
DOI: 10.1021/ja410747g

Abstract

The synthesis and full characterization of a well-defined silica-supported ≡Si-O-W(Me)5 species is reported. Under an inert atmosphere, it is a stable material at moderate temperature, whereas the homoleptic parent complex decomposes above -20 °C, demonstrating the stabilizing effect of immobilization of the molecular complex. Above 70 °C the grafted complex converts into the two methylidyne surface complexes [(≡SiO-)W(≡CH)Me2] and [(≡SiO-)2W(≡CH)Me]. All of these silica-supported complexes are active precursors for propane metathesis reactions.