The reactivity of CF3CO+ ions, formed via two different routes, has been studied in the gas phase by the joint use of mass spectrometric and radiolytic techniques, spanning a pressure range from Torr to ca. 1 atm. The 23 kcal/mol exothermic addition of CF3+ to CO provides a route to CF3CO+ requiring third-body stabilization of the adduct ion. In the Torr pressure regime of Fourier transform ion cyclotron resonance (FT-ICR) spectrometry, CF3CO+ ions from electron ionization (EI) induced fragmentation of trifluoroacetic anhydride yield NuCF3+ products from oxygen-centered nucleophiles (Nu) and XC6H4CO+ ions from aromatics (C6H5X). At ca. 1 atm trifluoroacetylated products are efficiently formed even with strongly deactivated aromatics, showing distinct intra- and intermolecular selectivity features pertaining to the reactant CF3CO+ ions. The reactivity pattern is interpreted according to a kinetic interplay of collisional and chemical events depending on the activation of C6H5X toward electrophilic attack.

Ion-Molecule Reactions in Gaseous CF4/CO Mixtures. Formation and Reactivity of CF3CO+ Ions / Cacace, Fulvio; Crestoni, Maria Elisa; Fornarini, Simonetta. - In: THE JOURNAL OF PHYSICAL CHEMISTRY. - ISSN 0022-3654. - STAMPA. - 98:(1994), pp. 1641-1647. [10.1021/j100057a017]

Ion-Molecule Reactions in Gaseous CF4/CO Mixtures. Formation and Reactivity of CF3CO+ Ions

CACACE, Fulvio;CRESTONI, Maria Elisa;FORNARINI, Simonetta
1994

Abstract

The reactivity of CF3CO+ ions, formed via two different routes, has been studied in the gas phase by the joint use of mass spectrometric and radiolytic techniques, spanning a pressure range from Torr to ca. 1 atm. The 23 kcal/mol exothermic addition of CF3+ to CO provides a route to CF3CO+ requiring third-body stabilization of the adduct ion. In the Torr pressure regime of Fourier transform ion cyclotron resonance (FT-ICR) spectrometry, CF3CO+ ions from electron ionization (EI) induced fragmentation of trifluoroacetic anhydride yield NuCF3+ products from oxygen-centered nucleophiles (Nu) and XC6H4CO+ ions from aromatics (C6H5X). At ca. 1 atm trifluoroacetylated products are efficiently formed even with strongly deactivated aromatics, showing distinct intra- and intermolecular selectivity features pertaining to the reactant CF3CO+ ions. The reactivity pattern is interpreted according to a kinetic interplay of collisional and chemical events depending on the activation of C6H5X toward electrophilic attack.
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Ion-Molecule Reactions in Gaseous CF4/CO Mixtures. Formation and Reactivity of CF3CO+ Ions / Cacace, Fulvio; Crestoni, Maria Elisa; Fornarini, Simonetta. - In: THE JOURNAL OF PHYSICAL CHEMISTRY. - ISSN 0022-3654. - STAMPA. - 98:(1994), pp. 1641-1647. [10.1021/j100057a017]
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11573/452899
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