Department of Chemistry and Applied Biosciences, ETH-Zürich, Vladimir Prelog Weg 2, CH-8093, Zürich (Switzerland).
Angew Chem Int Ed Engl. 2014 Dec 15;53(51):14221-4. doi: 10.1002/anie.201408880. Epub 2014 Oct 15.
The reaction of [W(=O)(=CHCMe2Ph)(dAdPO)2], containing bulky 2,6-diadamantyl aryloxide ligands, with partially dehydroxylated silica selectively yields a well-defined silica-supported alkylidene complex, [(≡SiO)W(=O)(=CHCMe2Ph)(dAdPO)]. This fully characterized material is a very active and stable alkene metathesis catalyst, thus allowing loadings as low as 50 ppm in the metathesis of internal alkenes. [(≡SiO)W(=O)(=CHCMe2Ph)(dAdPO)] also efficiently catalyzes the homocoupling of terminal alkenes, with turnover numbers exceeding 75,000 when ethylene is constantly removed to avoid the formation of the less reactive square-based pyramidal metallacycle resting state.
[W(=O)(=CHCMe2Ph)(dAdPO)2]的反应，其中含有体积庞大的 2,6-二金刚烷基芳氧基配体，与部分脱羟基的硅胶选择性地生成了一种结构明确的硅胶负载的亚烷基络合物，[(≡SiO)W(=O)(=CHCMe2Ph)(dAdPO)]。这种完全表征的材料是一种非常活跃和稳定的烯烃复分解催化剂，因此在内部烯烃的复分解中可以低至 50ppm 的负载量使用。[(≡SiO)W(=O)(=CHCMe2Ph)(dAdPO)]也能有效地催化末端烯烃的同系偶联，当不断除去乙烯以避免形成反应性较低的四方锥型金属络合物基态时，周转数超过 75,000。
