Novel Indenylzirconium Complexes as Supported Catalysts in the Polymerization of Ethylene

A series of substituted indene {C 9 H 7 R‐3 [R = CH 2 CH 2 CH 2 OSiMe 3 ( 1 ), CH 2 CH 2 CH 2 OCH 2 C 6 H 5 ( 2 ), CH 2 CH 2 CH 2 OSiMe 2 t Bu ( 3 )]}, and ansa ‐indene compounds {Me 2 Si(C 9 H 6 R‐3) 2 ‐1[R = CH 2 CH 2 CH 2 OSiMe 3 ( 4 )], Me 2 Si(C 9 H 6 R‐3)‐1(C 5 HMe 4 ) [R = CH 2 CH 2 CH 2 OSiMe 3 ( 5 ), CH 2 CH 2 CH 2 OCH 2 C 6 H 5 ( 6 ), CH 2 CH=CH 2 ( 7 ), CH 2 CH 2 CH 2 OSiMe 2 t Bu ( 8 )]} have been prepared. The lithium derivatives of 1 – 8 were employed in the synthesis of the indenylzirconium complexes [Zr(η 5 ‐C 9 H 6 R‐1) 2 Cl 2 ] [R = CH 2 CH 2 CH 2 OSiMe 3 ( 17 ), CH 2 CH 2 CH 2 OCH 2 C 6 H 5 ( 18 ), CH 2 CH 2 CH 2 OSiMe 2 t Bu ( 19 )], rac ‐[Zr{Me 2 Si(η 5 ‐C 9 H 5 R‐3) 2 ‐1}Cl 2 ] [R = CH 2 CH 2 CH 2 OSiMe 3 ( 20 )], [Zr{Me 2 Si(η 5 ‐C 9 H 5 R‐3)‐1(η 5 ‐C 5 Me 4 )}Cl 2 ] [R = CH 2 CH 2 CH 2 OSiMe 3 ( 21 ), CH 2 CH 2 CH 2 OCH 2 C 6 H 5 ( 22 ), CH 2 CH=CH 2 ( 23 ), CH 2 CH 2 CH 2 OSiMe 2 t Bu ( 24 )] and [Zr(Me 2 Si{η 5 ‐C 9 H 5 (CH 2 CH 2 CH 2 O)‐3}‐1{η 5 ‐C 5 Me 4 })Cl] ( 21a ). The alkyl complexes [Zr(Me 2 Si{η 5 ‐C 9 H 5 (CH 2 CH 2 CH 2 O)‐3}‐1{η 5 ‐C 5 Me 4 })Me] ( 25 ) and [Zr{Me 2 Si(η 5 ‐C 9 H 5 R‐3)‐1(η 5 ‐C 5 Me 4 )}Me 2 ] [R = CH 2 CH 2 CH 2 OSiMe 2 t Bu ( 26 )] have been synthesized by the reaction of the corresponding ansa ‐zirconocene derivative with the alkyl Grignard reagent. The molecular structure of [(Zr{C 9 H 6 (CH 2 CH 2 CH 2 O)‐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, 69451 Weinheim, Germany, 2005)