Vanadium Imido NHC Complexes for Ring-Closing Olefin Metathesis Reactions
Gabriela Tejeda, Dmitry S. Belov, Dídac A. Fenoll, Kelly L. Rue, Charlene Tsay, Xavier Solans‐Monfort, Konstantin V. Bukhryakov
Abstract
Vanadium bis-phosphine imido and oxo chloride alkylidenes have been extensively applied in the ring-closing metathesis of various acyclic olefins. However, their reactions involving ethylene have shown limited productivity due to rapid decomposition. The primary degradation pathway involving V bis-phosphine imido complexes is β-H elimination at an unsubstituted metallacyclobutane. In contrast, β-H elimination is disfavored for V oxo species, but bimolecular decomposition precludes its high productivity. Herein, we present the synthesis of V imido NHC complexes that are the most productive V catalysts toward various terminal olefins in ring-closing metathesis reactions. Experimental and computational studies suggest that β-H elimination and bimolecular decomposition are disfavored for V imido NHC complexes.