Benzylidene-Functionalized Ruthenium-Based Olefin Metathesis Catalysts for Ring-Opening Metathesis Polymerization in Organic and Aqueous Media

Abstract

New catalysts (PCy 3 ) 2 Cl 2 Ru═CH( p -C 6 H 4 )CH 2 -P(CH 3 ) 3 + Cl − ( 5 ) and (PCy 3 ) 2 Cl 2 Ru═CH( p -C 6 H 4 )CH 2 -N(CH 3 ) 2 ( 6 ) as well as the literature compound (PCy 3 ) 2 Cl 2 Ru═CH( p -C 6 H 4 )N(CH 3 ) 2 ( 7 ) have been synthesized via alkylidene exchange from Grubbs’ catalyst in a one-step reaction. The catalysts promoted ROMP of the cationic exo -7-oxanorbornene derivative 11 under homogeneous conditions in various protic media including aqueous/alcoholic 1:1 mixtures, and in many cases, particularly for catalysts 5 and 6, the polymerizations proceeded in a controlled manner.