Novel indenylzirconium complexes as supported catalysts in the polymerization of ethylene

Abstract

A series of substituted indene {C9H7R-3 [R = CH 2CH2CH2OSiMe3 (1), CH 2CH2CH2OCH2C6H 5 (2), CH2CH2CH2OSiMe2tBu (3)]}, and ansa-indene compounds {Me2Si(C9H 6R-3)2-1 [R = CH2CH2CH 2OSiMe3 (4)], Me2Si(C9H 6R-3)-1(C5HMe4) [R = CH2CH 2CH2OSiMe3 (5), CH2CH 2CH2OCH2C6H5 (6), CH 2CH=CH2 (7), CH2CH2CH 2OSiMe2tBu (8)]} have been prepared. The lithium derivatives of 1-8 were employed in the synthesis of the indenylzirconium complexes [Zr(η5-C9H6R-1) 2Cl2] [R = CH2CH2CH 2OSiMe3 (17), CH2CH2CH 2OCH2C6H5 (18), CH 2CH2CH2OSiMe2tBu (19)], rac-[Zr{Me2Si(η5-C9H5R-3) 2-1}Cl2] [R = CH2CH2CH 2OSiMe3 (20)], [Zr{Me2Si(η5- C9H5R-3)-1(η5-C5Me 4)}Cl2] [R = CH2CH2CH 2OSiMe3 (21), CH2CH2CH 2OCH2C6H5 (22), CH 2CH=CH2 (23), CH2CH2CH 2OSiMe2tBu (24)] and [Zr(Me2Si{η 5-C9H5(CH2CH2CH 2O)-3}-1{η5-C5Me4})Cl] (21a). The alkyl complexes [Zr(Me2Si{η5-C9H 5(CH2CH2CH2O)-3}- 1{η5-C5Me4})Me] (25) and [Zr{Me 2Si(η5-C9H5R-3)- 1(η5-C5Me4)}Me2] [R = CH 2CH2CH2OSiMe2tBu (26)] have been synthesized by the reaction of the corresponding ansa-zir-conocene derivative with the alkyl Grignard reagent. The molecular structure of [(Zr{C 9H6(CH2CH2CH2O)-1}Cl 2)2(Zr-O)] (17a), a subproduct in the formation of 17 has been determined by single-crystal X-ray diffraction studies. The indenylzirconium complexes 17-24 have been immobilized on partially dehydroxylated SiO 2, and these supported systems used to polymerize ethylene in the presence of methylaluminoxane. The catalytic activity of these compounds in both homogeneous and heterogeneous polymerization is reported. © Wiley-VCH Verlag GmbH & Co. KGaA, 2005.