Key intermediates in metallocene-and post-metallocene-catalyzed polymerization

The structures of intermediates formed upon the activation by methylaluminoxane (MAO) of a wide range of metallocene and post-metallocene catalysts of olefin polymerization were studied by C-13, H-1, and F-19 NMR. For all metallocenes considered (L2ZrCl2 and L2TiCl2), under conditions similar to real polymerization conditions (Al/Zr > 200), two types of intermediates were identified in the reaction solution, namely, heterodinuclear ion pairs [L-2 M(mu-Me)(2)AlMe2](+)[Me-MAO](-) (III) and zwitterionic intermediates L-2 MMe

Formation and Structures of Hafnocene Complexes in MAO- and AlBui3/CPh3[B(C6F5)4]-Activated Systems

The formation of cationic species relevant to olefin polymerization based on (SBI)HfCl2, Me2C(C5H4)(Flu)HfCl2, Ph2C(C5H4)(Flu)HfCl2, and L'HfCl2 activated by MAO, AlMe3/CPh3[B(C6F5)4], and AlBui3/CPh3[B(C6F5)4] (SBI = rac-Me2Si(Ind)2; L' = C2H4(Flu)(5,6-C3H6-2-MeInd)) was studied by 1H, 13C, and 19F NMR spectroscopy. Thermally stable heterobinuclear intermediates of the type [LHf(µ-Me)2AlMe2]+[MeMAO]- and [LHf(µ-Me)2AlMe2]+[B(C6F5)4]- were identified when using MAO and AlMe3/CPh3[B(C6F5)4] as activators, respectively. The stability of these species explains the low productivity of hafnocene catalysts in the presence of AlMe3-containing activators, compared to zirconocenes. By contrast, in the ternary systems LHfCl2/AlBui3/CPh3[B(C6F5)4] hydride species were detected that must be responsible for the formation of the highly active sites in olefin polymerization. The ionic hydrido species differ significantly in stability. The formation of the mixed-alkyl complex L'Hf(Me)CH2SiMe3 proceeds with surprisingly high diastereoselectivity; the sterically more hindered isomer is produced preferentially. It reacts with CPh3[B(C6F5)4] to afford the ion pair [L'Hf-CH2SiMe3]+[B(C6F5)4]- as two diastereomers that exist in dynamic equilibrium. The rates of site epimerization of this ion pair indicate only small energy differences between the two isomers