Artículos de revistas
Reactions Of Gaseous Halocarbonyl Cations With Aromatic Compounds: Ionic Carbonylation Of Inert C-h Bonds
Registro en:
International Journal Of Mass Spectrometry. , v. 228, n. 02/03/15, p. 901 - 912, 2003.
13873806
10.1016/S1387-3806(03)00239-2
2-s2.0-0041705024
Autor
Da Rocha L.L.
Sparrapan R.
Eberlin M.N.
Institución
Resumen
The mass-selected halocarbonyl cations FCO+, ClCO+, and BrCO+ were reacted with benzene, thiophene, pyrrole, and furan and a few of their alkyl derivatives to evaluate the ability of XCO+ ions to promote C-H bond activation of aromatic compounds (M-H) via gas-phase ionic carbonylation. This novel reaction occurs via electrophilic addition followed by prompt HX elimination, forms the respective acylium ions (M-CO+), and competes with electron abstraction and X+ transfer. The intrinsic gas-phase reactivity order observed for ionic carbonylation was: FCO+>ClCO+>BrCO+. The ability of the fluorosulfinyl cation (FSO+) to promote analogous ionic sulfonylation of aromatic compounds was also tested, but owing to its high recombination energy, FSO+ acts as a potent oxidizing agent and electron abstraction dominates. A novel, highly efficient and nearly exclusive O-abstraction reaction of FC+ and SF+ with N2O was used to the straightforward preparation of gaseous FCO+ and SFO+. 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