Heterocycle‐Substituted Indenes as Precursors for Supported Zirconocene Catalysts

The indene ligands {1‐C 9 H 7 R} [R = C 2 H 4 (C 4 H 7 O 2 ) ( 1 ), C 2 H 4 (C 3 H 5 O 2 ) ( 2 ), CH 2 (C 5 H 9 O) ( 3 )] were prepared by alkylation of indene and used to prepare the SiMe 2 ‐bridged indenylcyclopentadiene ligands {Me 2 Si(3‐C 9 H 6 R)(C 5 Me 4 H)}[R = C 2 H 4 (C 4 H 7 O 2 ) ( 4 ), CH 2 (C 5 H 9 O) ( 5 )]. Bis(indenyl)‐and ansa ‐indenylcyclopentadienyl zirconocenes [Zr{1‐η 5 ‐C 9 H 6 R} 2 Cl 2 ] {R = C 2 H 4 (C 4 H 7 O 2 ) ( 6 ), C 2 H 4 (C 3 H 5 O 2 ) ( 7 ), CH 2 (C 5 H 9 O) ( 8 )} and [Zr{Me 2 Si(3‐η 5 ‐C 9 H 5 R)(η 5 ‐C 5 Me 4 )}Cl 2 ] {R = C 2 H 4 (C 4 H 7 O 2 ) ( 9 ), CH 2 (C 5 H 9 O) ( 10 )} were prepared by the reaction of ZrCl 4 with the appropriate mono‐ or dilithium salts of 1 – 5 . The molecular structure of [Zr{Me 2 Si(3‐η 5 ‐C 9 H 5 C 2 H 4 (C 4 H 7 O 2 ))(η 5 ‐C 5 Me 4 )}Cl 2 ] ( 9 ) was determined by single‐crystal X‐ray diffraction studies. Indenylzirconium complexes 6 – 10 were immobilized on thf‐modified MgCl 2 , and these supported systems were used to polymerize ethylene in the presence of methylaluminoxane. The catalytic activity of these complexes in both homogeneous and supported polymerization reactions is discussed. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)