W-oxo Adamantylidenes: Stable Molecular Precursors for Efficient Silica-Supported Metathesis Catalysts
Abstract
Tungsten oxo adamantylidenes (=Ad) are a new class of readily accessible alkylidenes, that opens the possibility to evaluate a broader class of molecular and supported olefin metathesis catalysts. In this context, W(O)(=Ad)X2, with X=pyrrolide and perfluoro-tert-butoxide, were grafted on partially dehydroxylated silica, to generate the corresponding silica-supported tungsten oxo adamantylidenes. The high thermal stability of the molecular perfluoro-tert-butoxide complex, that exists as a dimer in the solid state, even enables its grafting through sublimation. Evaluation of their catalytic activities toward olefin metathesis using standardized protocols show that these supported species display high activity toward internal and terminal olefins. In particular, avoiding the use of solvent during grafting of the highly electrophilic perfluoro-tert-butoxide compounds, that can bind to the W center, enable to generate significantly more active catalysts. Show more
Permanent link
https://doi.org/10.3929/ethz-b-000538582Publication status
publishedExternal links
Journal / series
Helvetica Chimica ActaVolume
Pages / Article No.
Publisher
Wiley-VCHSubject
adamantylidenes; olefin metathesis; surface chemistry; surface organometallic chemistry; tungstenOrganisational unit
03872 - Copéret, Christophe / Copéret, Christophe
Funding
169134 - Molecular Approach to Heterogeneous Catalysis (SNF)
192050 - Molecular Approach and Understanding in Heterogeneous Catalysis (SNF)
More
Show all metadata