Fluorenyl based syndiotactic specific metallocene catalysts structural features,origin of syndiospecificity |
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Authors: | Abbas Razavi Vincenzo Bellia Yves De Brauwer Kai Hortmann Liliane Peters Sabine Sirole Stephan Van Belle Ulf Thewalt |
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Institution: | 1. Atofina Research S.A., Centre de Recherche Du Groupe Total, Zone Industrielle C, B-7181 Seneffe (Feluy), Belgium;2. Sektion für Röntgen und Elektronenbeugung Universität Ulm, Germany |
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Abstract: | The stereochemistry of propylene insertion/propagation reactions with a variety of Cs symmetric fluorenyl- containing single site catalysts is discussed. Our recent results indicate that independent of the chemical composition of the ancillary ligand fragments, or nature of the transition metal, active sites with local Cs symmetry and enantiotopic coordination positions behave syndioselectively in the general context of chain migratory insertion mechanism. Perfect bilateral symmetry neither exists nor is required in these processes. In this context the mechanism of syndiospecific polymerization is revisited by taking into account the structural characteristics and catalytic behavior of the original metallocene based (η5-C5H4-CMe2-η5-C13H8) MCl2/ MAO; M = Zr ( 1 ), Hf ( 2 ) catalyst systems and new syndiotactic specific systems including (η5-C5H4-CPh2-η5-3,6-di-tBut-C13H6)ZrCl2 ( 3 ), η1,η5-(μMe2Si)(3,6-di-tBut-Flu)(t-ButN)MCl2/ MAO; M =Ti ( 4 ), Zr ( 5 ) and η1,η5-(μMe2Si)(2,7-di-tBut-Flu)(t-ButN)MCl2/ MAO; M = Ti ( 6 ), Zr ( 7 ). |
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Keywords: | catalysis mechanism metallocene polypropylene syndiospecificity |
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