Bisphosphine Monoxide-Ligated Ruthenium Catalysts: Active, Versatile, Removable, and Cocatalyst-Free in Living Radical Polymerization

As potentially bidentate ligands, bisphosphine monoxides [BPMOs; Ph2P(O)(CH2)nPPh2; n = 1, 2; Ph = C6H5] were found to be effective for pentamethylcyclopentadiene ruthenium chloride catalysts [Cp*RuIICl(BPMO)m; m = 1,2] in living radical polymerization: active, versatile, cocatalyst-free, and removable. The complexes catalyzed living radical polymerizations of a variety of monomers and their functionalized derivatives: methyl acrylate, methyl methacrylate (MMA), styrene, 2-hydroxyethyl methacrylate, and poly(ethylene glycol) methacrylate. The controllability and activity were high enough even with a small amount of catalyst ([Ru]0/[initiator]0 = 1/200; 50 ppm for monomer), to give high molecular weight PMMA with narrow MWD (Mn = 103 000: Mw/Mn = 1.19) and block copolymers. Such an activity and a wide applicability in terms of monomers have been found for few Ru catalysts thus far. Importantly, they did not necessarily need a cocatalyst (aluminum alkoxide, amine, etc.) for their catalysis, in contrast to most of the other ruthenium catalysts that are effective only with a cocatalyst. The cocatalyst-free catalysis is concluded to be derived from the phosphine oxide moiety in BPMO, whose hemilabile coordination promotes the deactivation process [∼∼∼C• (growth active) → ---C−Cl (dormant)] and, in turn, accelerates the whole catalytic cycle (radical ↔ dormant; RuII ↔ RuIII). Furthermore, the high polarity of BPMO ligands effectively helped near perfect removal of the catalyst residue (>99.7% for PMMA) just by single reprecipitation into methanol.