Copolymerization of Ethylene with Norbornene Catalyzed by Cationic Rare-Earth Metal Half-Sandwich Complexes

Abstract

We report on copolymerizations of ethylene with norbornene with half-sandwich rare-earth metal catalysts generated by activation of dialkyl complexes [Ln(η5-C5Me4SiMe2R)(η1-CH2SiMe3)2(THF)] (Ln = Sc, R = Me (1); Ln = Sc, R = C6F5 (2); Ln = Y, R = C6F5 (3); Ln = Lu, R = C6F5 (4)) with [Ph3C][B(C6F5)4]. Complexes 1 and 2 showed excellent activities, whereas complex 3 gave poor activity and 4 was practically inactive. Weak stabilization of metal center by bulkier silyl group of the tetramethylcyclopentadienyl ring in complexes 2 and 3 allows controlled copolymerization (Mw/Mn < 1.3). Mainly atactic alternating P(E-co-N) copolymers were obtained with the active catalytic systems. These copolymerizations were well described by first-order Markov statistics.