Collect. Czech. Chem. Commun. 2007, 72, 747-763

Synthesis of Bulky Zirconocene Dichloride Compounds and Their Applications in Olefin Polymerization

Dorian Polo-Ceróna, Santiago Gómez-Ruiza, Sanjiv Prashara,*, Mariano Fajardoa, Antonio Antiñolob and Antonio Oterob

a Departamento de Química Inorgánica y Analítica, E.S.C.E.T., Universidad Rey Juan Carlos, 28933 Móstoles (Madrid), Spain
b Departamento de Química Inorgánica, Orgánica y Bioquímica, Facultad de Químicas, Campus Universitario, Universidad de Castilla-La Mancha, 13071-Ciudad Real, Spain


The bulky substituted cyclopentadienyllithium derivatives, LiC5H4(CHMeR) (R = C6H5 (1), 1-naphthyl (2), 9-anthryl (3)), were synthesized from the reaction of 6-phenylfulvene, 6-(1-naphthyl)fulvene or 6-(9-anthryl)fulvene with LiMe. The ansa-bis(cyclopentadiene) ligands Me2Si(C5HMe4){C5H4(CHMeR)} (R = C6H5 (4), 1-naphthyl (5), 9-anthryl (6)), and their lithium derivatives Li2(Me2Si(C5Me4){C5H3(CHMeR)}) (R = C6H5 (7), 1-naphthyl (8), 9-anthryl (9)) have been prepared. The zirconocene complexes, [Zr(η5-C5H5){η5-C5H4- (CHMeR)}Cl2] (R = C6H5 (10), 1-naphthyl (11), 9-anthryl (12)) and [Zr{η5-C5H4(CHMeR)}2Cl2] (R = C6H5 (13), 1-naphthyl (14), 9-anthryl (15)), were synthesized by the reaction of lithium derivatives 1-3 and [Zr(η5-C5H5)Cl3] or ZrCl4, respectively. The reaction of the lithium ansa-derivatives 7-9 and zirconium tetrachloride yielded the ansa-zirconocene complexes, [Zr(Me2Si(η5-C5Me4){η5-C5H3(CHMeR)})Cl2] (R = C6H5 (16), 1-naphthyl (17), 9-anthryl (18)). The zirconocene complexes have been tested in the polymerization of ethene and propene. The polymerization of propene with the ansa-zirconocene catalysts 16-18 gave polypropylene with 70% mmmm pentads and the symmetric zirconocene catalysts 13-15 30-60% mmmm pentads.

Keywords: Metallocenes; Zirconocenes; Zirconium; Polymerization; Polyethylene; Polypropylene; Lewis acids.

References: 36 live references.