| Abstract
| - Effects of additives (metal alkoxides and halides) were investigated in the RuCl2(PPh3)3-catalyzed living radical polymerization of methyl methacrylate (MMA) in toluene at 80 °C. While theMMA polymerization with the RuCl2(PPh3)3/CCl4 system (CCl4: initiator) is very slow and producespolymers with broad molecular weight distributions (MWDs), addition of metal alkoxides, such as Al(Oi-Pr)3, Ti(Oi-Pr)4, and Sn(Oi-Pr)4, accelerated the polymerization to produce polymers with controlledmolecular weights and narrow MWDs. Metal chlorides such as SnCl4 and TiCl4 were not effective additives.According to NMR and cyclic voltammetric analyses, Al(Oi-Pr)3 does not interact with monomer or thepolymer termini (∼∼∼C−Cl and ∼∼∼C• radicals) but interacts with the ruthenium complex, or morelikely, its higher oxidation state Ru(III) species.
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