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Asymmetric binuclear metallocene complexes and their application for olefin polymerization


Correspondence to: J. Huang (E-mail:


Asymmetric double silylene-bridged binuclear complexes [(η5-RC5H4)MCl2]2[μ, μ-(SiMe2)25-t-BuC5H2)(η5-C5H3)][R = H, M = Ti (1); R = Me, M = Ti (2); R = allyl, M = Ti(3); R = H, M = Zr (4); R = allyl, M= Zr (6)]; and [(η5-C5H5)TiCl2]2[μ, μ-(SiMe2)25-Me3SiC5H2)(η5-C5H3)] (5) were synthesized by the reaction of (η5-RC5H4) TiCl3 or (η5-RC5H4)ZrCl3·DME (R = H, allyl) with [μ, μ- (SiMe2)25-t-BuC5H2)(η5-C5H3)] Li2 or [μ, μ-(SiMe2)25-Me3Si C5H2)(η5-C5H3)]Li2 in THF, and they were all well characterized by 1H NMR, MS, IR, and EA. When activated with methylaluminoxane (MAO), they are efficient catalysts for the polymerization of ethylene (Complex 4, 5.99 × 105 g-PE/mol·Zr·h) and the polymer with multipeak broaden molecular weight distribution (PD = Mw/Mn) was obtained (polymer sample gained by complex 3, PD = 25.03). The copolymerization results indicate that 1-hexene could incorporate into the growing PE chain with these complexes in the presence of MAO (Complex 4, 1.07 × 106 g-PE/mol·Zr·h; 1-hexene content, 1.57% mol). © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2891–2900, 2013