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  • Gas-phase reactions of the bis(η5-cyclopentadienyl)methylzirconium cation with imines
  • Add time:08/16/2019         Source:sciencedirect.com

    The reactions of the bis(η5-cyclopentadienyl)methylzirconium cation (1) with four imines have been studied in the gas phase by Fourier transform ion cyclotron resonance mass spectrometry. Reactivity of the bis(η5-cyclopentadienyl)methylzirconium cation is governed by the availability of a labile hydrogen in the corresponding imine. The products observed differ from those that might be expected in analogy with earlier work on ketones, aldehydes and alkenes (e.g., zirconocene η3-enolate and η3-allyl complexes): azomethyne/benzylidene species are found instead of enamines; however, the general reaction mechanism resembles that proposed for ketones and alkenes. An elimination reaction leading to final products was shown to be preceded by a fast migratory insertion/deinsertion equilibrium for alkyl-substituted imines. Such an equilibrium is not possible for aryl-substituted imines due to lack of lability of the aryl groups and thus only methane elimination was observed for these imines.

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