Half-zirconocene anilide complexes: synthesis, characterization and catalytic properties for ethylene polymerization and copolymerization with 1-hexene.

A number of half-zirconocene anilide complexes of the type Cp*ZrCl(2)[N(2,6-R(1)(2)C(6)H(3))R(2)] [R(1) = (i)Pr (1, 3), Me (2); R(2) = Me (1, 2), Bn (3)] and Cp*ZrCl[N(2,6-Me(2)C(6)H(3))Me](2) (4) (Cp* = pentamethylcyclopentadienyl) were synthesized from the reactions of Cp*ZrCl(3) with the lithium salts of the corresponding anilide in diethyl ether at room temperature. All new zirconium complexes were characterized by (1)H and (13)C NMR and elemental analysis. Molecular structures of complexes 1, 2 and 4 were determined by single crystal X-ray diffraction analysis. Upon activation with Al(i)Bu(3) and Ph(3)CB(C(6)F(5))(4), complexes 1-4 exhibit good catalytic activity for ethylene polymerization, and produce polyethylene with a moderate molecular weight. Among these zirconium complexes, complex 1 shows the highest catalytic activity while complex 4 shows the lowest catalytic activity for ethylene polymerization. Complexes 1-3 also exhibit moderate catalytic activity for copolymerization of ethylene with 1-hexene, and produce copolymers with relatively high molecular weight and reasonable 1-hexene incorporation. In addition, the activation procedure of these catalyst systems were studied by (1)H NMR spectroscopy.