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The C-D activation of bromobenzene-d(5) by [Cp*(2)ZrMe(BrC(6)D(5)-kappaBr)][B(C(6)F(5))(4)] to form sigma-aryl complex [Cp*(2)Zr(2-BrC(6)D(4)-kappa(2)Br,C)][B(C(6)F(5))(4)] is accelerated when the decamethylzirconocene methyl cation is generated in the presence of tertiary amines. Computational studies suggest that the overall sigma-bond metathesis reaction proceeds, in the presence of tertiary amines, via initial deprotonation of bromobenzene in the coordination sphere of the metal center. In a subsequent step, the resulting neutral methyl aryl species, Cp*(2)ZrMe(2-BrC(6)D(4)), reacts with the concurrently generated trialkylammonium cation to generate [Cp*(2)Zr(2-BrC(6)D(4)-kappa(2)Br,C)][B(C(6)F(5))(4)].

Amine Catalyzed Solvent C−H Bond Activation as Deactivation Route for Cationic Decamethylzirconocene Olefin Polymerization Catalysts