Metathesis of Classical and Functionalized Olefins Catalyzed by Silica‐Supported Single‐Site Well‐Defined W and Mo Pre‐catalysts

Aya Saidi, Manoja K. Samantaray, Albert Poater, Mykyta Tretiakov, Jean-Marie Basset, Luigi Cavallo
ChemCatChem, (2020)


Surface organometallic chemistry, Catalysis, Olefin metathesis, Functionalized olefin metathesis, Organometallic


​Olefin metathesis of α‐olefins (C 6 , C 8 , C 10 ), α, β‐unsaturated ester, α, β‐ unsaturated acetate and cross‐metathesis of 1‐octene and ethyl 6‐heptenoate were carried out using well‐defined [(≡Si‐O‐)W(CH 3 ) 5 ] and [(≡Si‐O‐)Mo(≡C t Bu)(CH 2 t Bu) 2 ] pre‐catalysts. During the reaction, it was observed that irrespective of the chain length, linear α‐olefins are almost showing similar TON. We observed that Mo pre‐catalyst performs better with TONs between 700 and 1478 as compared to W with TONs between 213 and 962 at room temperature. Both the pre‐catalysts performed equally at 70 ᴼ C, with almost similar activity as well as TON (≈ 1700). We also carried out self‐metathesis of functionalized olefins using both silica‐supported W and Mo pre‐catalysts. It was observed that W pre‐catalyst performs much better than Mo pre‐catalyst for functionalized olefin metathesis reaction in our conditions. Additionally, we noticed that W pre‐catalyst provides selective metathesis product, whereas Mo pre‐catalyst gives a range of products due to the isomerization of the olefinic bond.



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