Decomposition of a Phosphine-Free Metathesis Catalyst by Amines and Other Bronsted Bases: Metallacyclobutane Deprotonation as a Major Deactivation Pathway

Reactions are described of the second-generation Hoveyda catalyst HII with amines, pyridine, and DBU (1,8-diazabicyclo[5.4.0]undec-7-ene), in the presence and absence of olefin substrates. These nitrogen bases have a profoundly negative impact on metathesis yields, but in most cases, they are innocuous toward the precatalyst. HII adducts were formed by primary and secondary amines (n-butylamine, sec-butylamine, benzylamine, pyrrolidine, morpholine), pyridine, and DBU at room temperature. No reaction was evident for NEt3, even at 60 °C. On longer reaction at RT, unencumbered primary amines abstract the benzylidene ligand from HII. With 10 equiv of NH2nBu, this process was complete in 12 h, affording NHnBu(CH2Ar) (Ar = o-C6H4–OiPr) and [RuCl(H2IMes)(NH2nBu)4]Cl. For benzylamine, benzylidene abstraction occurred over days at RT. No such reaction was observed for sec-butylamine, secondary amines, NEt3, pyridine, or DBU. All of these bases, however, strongly inhibited metathesis of styrene by HII, with a gener...