Abstract
We present the cationic Cp*–ruthenium complexes [Cp*Ru(CH3CN)(PPh3)2A; A–: the counteranion; abbreviated Cp*Ru+A–] as the active, cocatalyst-free, and tunable catalysts for metal-catalyzed living radical polymerization (Mt-LRP). A PF6-based cationic complex in conjunction with a alkyl halide initiator led to controlled polymerization of methyl methacrylate (MMA) giving well-controlled PMMAs with narrow molecular weight distribution (Mw/Mn 80% in 15 h), although cocatalyst was not combined. The catalytic feature was clearly different from the neutral counterpart [Cp*RuCl(PPh3)2: Cp*Ru], resulting in retarded polymerization under the cocatalyst-free condition. Interestingly, the catalytic activity was influenced by the counteranions. For example, the PF6-based complex did not afford catalysis for controlled polymerization of methyl acrylate (MA), but an Sb6-based [Cp*Ru(CH3CN)(PPh3)2SbF6: Cp*Ru+SbF6–] allowed control of the polymerization. Model reacti...
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