Probing Catalyst Degradation in Metathesis of Internal Olefins: Expanding Access to Amine-Tagged ROMP Polymers

Abstract

Ruthenium-promoted ring-opening metathesis polymerization (ROMP) offers potentially powerful routes to amine-functionalized polymers with antimicrobial, adhesive, and self-healing properties. However, amines readily degrade the methylidene and unsubstituted ruthenacyclobutane intermediates formed in metathesis of terminal olefins. Examined herein is the relevance of these decomposition pathways to ROMP (i.e., metathesis of internal olefins) by the third-generation Grubbs catalyst. Primary alkylamines rapidly quench polymerization via fast adduct formation, followed by nucleophilic abstraction of the propagating alkylidene. Bulkier, Brønsted-basic amines are less aggressive: attack competes only for slow polymerization or strong bases (e.g., DBU). Added HCl limits degradation, as demonstrated by the successful ROMP of an otherwise intractable methylamine monomer.