title: Amine catalyzed solvent C-H bond activation as deactivation route for cationic decamethylzirconocene olefin polymerization catalysts.
abstract: 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)].
authors.affiliation: Molecular Inorganic Chemistry, Stratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands.
authors.forename: Itzel Guerrero
authors.initials: IG
authors.lastname: Rios
authors.forename: Elena
authors.initials: E
authors.lastname: Novarino
authors.forename: Siebe
authors.initials: S
authors.lastname: van der Veer
authors.forename: Bart
authors.initials: B
authors.lastname: Hessen
authors.forename: Marco W
authors.initials: MW
authors.lastname: Bouwkamp