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

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• 作者：Itzel Guerrero Rios ; Elena Novarino ; Siebe van der Veer ; Bart Hessen ; Marco W. Bouwkamp
• 刊名：Journal of the American Chemical Society
• 出版年：2009
• 出版时间：November 25, 2009
• 年：2009
• 卷：131
• 期：46
• 页码：16658-16659
• 全文大小：155K
• 年卷期：v.131,no.46(November 25, 2009)
• ISSN：1520-5126

文摘

The C-D activation of bromobenzene-d₅ by [Cp*₂ZrMe(BrC₆D₅-κBr)][B(C₆F₅)₄] to form σ-aryl complex [Cp*₂Zr(2-BrC₆D₄-κ²Br,C)][B(C₆F₅)₄] is accelerated when the decamethylzirconocene methyl cation is generated in the presence of tertiary amines. Computational studies suggest that the overall σ-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*₂ZrMe(2-BrC₆D₄), reacts with the concurrently generated trialkylammonium cation to generate [Cp*₂Zr(2-BrC₆D₄-κ²Br,C)][B(C₆F₅)₄].