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 are innocuous toward the pre-catalyst. 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 NEt 3 , even at 60 °C. On longer reaction at RT, unencumbered primary amines abstract the benzylidene ligand from HII. With 10 equiv NH 2 n Bu, this process was complete in 12 h, affording NH n Bu(CH 2 Ar) (Ar = o-C 6 H 4 -O i Pr) and [RuCl(H 2 IMes)(NH 2 n Bu) 4 ]Cl. For benzylamine, benzylidene abstraction occurred over days at RT. No such reaction was observed for sec-butylamine, secondary amines, NEt 3 , pyridine, or DBU. All of these bases, however, strongly inhibited metathesis of styrene by HII, with a general trend toward more deleterious effects with higher Bronsted basicity. Studies at 10 mol% HII and 10 equiv DBU, NEt 3 , and pyrrolidine (60 °C, C 6 D 6 ) indicated that the primary mechanism for decomposition involved base-induced deprotonation of the metallacyclobutane intermediate, rather than the Lewis base-mediated decomposition pathways previously established for the Grubbs catalysts. In the corresponding metathesis of ethylene, this decomposition process is rapid even at RT, highlighting the vulnerability of the monosubstituted metallacyclobutane.
