Formation and Structures of Hafnocene Complexes in MAO- and AlBu<sup>i</sup><sub>3</sub>/CPh<sub>3</sub>[B(C<sub>6</sub>F<sub>5</sub>)<sub>4</sub>]-Activated Systems BryliakovKonstantin P. TalsiEvgenii P. VoskoboynikovAlexander Z. LancasterSimon J. BochmannManfred 2008 The formation of cationic species relevant to olefin polymerization based on (SBI)HfCl<sub>2</sub>, Me<sub>2</sub>C(C<sub>5</sub>H<sub>4</sub>)(Flu)HfCl<sub>2</sub>, Ph<sub>2</sub>C(C<sub>5</sub>H<sub>4</sub>)(Flu)HfCl<sub>2</sub>, and L′HfCl<sub>2</sub> activated by MAO, AlMe<sub>3</sub>/CPh<sub>3</sub>[B(C<sub>6</sub>F<sub>5</sub>)<sub>4</sub>], and AlBu<sup>i</sup><sub>3</sub>/CPh<sub>3</sub>[B(C<sub>6</sub>F<sub>5</sub>)<sub>4</sub>] (SBI = <i>rac</i>-Me<sub>2</sub>Si(Ind)<sub>2</sub>; L′ = C<sub>2</sub>H<sub>4</sub>(Flu)(5,6-C<sub>3</sub>H<sub>6</sub>-2-MeInd)) was studied by <sup>1</sup>H, <sup>13</sup>C, and <sup>19</sup>F NMR spectroscopy. Thermally stable heterobinuclear intermediates of the type [LHf(μ-Me)<sub>2</sub>AlMe<sub>2</sub>]<sup>+</sup>[MeMAO]<sup>−</sup> and [LHf(μ-Me)<sub>2</sub>AlMe<sub>2</sub>]<sup>+</sup>[B(C<sub>6</sub>F<sub>5</sub>)<sub>4</sub>]<sup>−</sup> were identified when using MAO and AlMe<sub>3</sub>/CPh<sub>3</sub>[B(C<sub>6</sub>F<sub>5</sub>)<sub>4</sub>] as activators, respectively. The stability of these species explains the low productivity of hafnocene catalysts in the presence of AlMe<sub>3</sub>-containing activators, compared to zirconocenes. By contrast, in the ternary systems LHfCl<sub>2</sub>/AlBu<sup>i</sup><sub>3</sub>/CPh<sub>3</sub>[B(C<sub>6</sub>F<sub>5</sub>)<sub>4</sub>] 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)CH<sub>2</sub>SiMe<sub>3</sub> proceeds with surprisingly high diastereoselectivity; the sterically more hindered isomer is produced preferentially. It reacts with CPh<sub>3</sub>[B(C<sub>6</sub>F<sub>5</sub>)<sub>4</sub>] to afford the ion pair [L′Hf-CH<sub>2</sub>SiMe<sub>3</sub>]<sup>+</sup>[B(C<sub>6</sub>F<sub>5</sub>)<sub>4</sub>]<sup>−</sup> 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.