Nickel-mediated polymerization of methyl methacrylate

• Novel complex [Ni(η5-C5H3R2)(Cl)(SIMes)] was synthesized and characterized.
• Complexes [Ni(Cp)(X)(NHC)] combined with MAO polymerize methyl methacrylate.
• Syndiotactic-rich, high molecular weight PMMAs were obtained.
• Coordinative-anionic, Al-centered mechanism of MMA polymerization is suggested.

The Ni(II) complexes [Ni(η5-C5H3R2)(X)(NHC)] 1a–f combined with MAO have been tested in methyl methacrylate (MMA) polymerization. We have found that the most active complex 1f, bearing the bulky 2,6-diisopropenylphenyl substituents in the NHC ligand, effected the MMA polymerization with TOF up to 200 h−1. Predominantly syndiotactic, high molecular weight PMMAs were obtained suggesting an anionic, MAO-centered polymerization mechanism.

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