Synthesis of Vanadium Oxo Alkylidene Complex and Its Reactivity in Ring-Closing Olefin Metathesis Reactions
Dmitry S. Belov, Dídac A. Fenoll, Indranil Chakraborty, Xavier Solans‐Monfort, Konstantin V. Bukhryakov
Abstract
V imido alkylidenes have been applied for the ring-opening metathesis polymerization involving cyclic olefins. However, those complexes found limited application in reactions with acyclic terminal olefins due to instability toward ethylene. Experimental and theoretical studies show that the β-hydride elimination from unsubstituted metallacyclobutene is the primary decomposition pathway in those systems. Herein, we report the synthesis of the first catalytically active V oxo alkylidene, VO(CHSiMe3)(PEt3)2Cl, which exhibits the highest reported productivity with various terminal olefins in ring-closing metathesis reactions among known V catalysts. Presented DFT studies indicate that β-hydride elimination is significantly disfavored for V oxo species.