The activation of C-halogen bonds of CH2Cl2 and CH2F2 by the SO•+ radical cation is investigated in the gas phase. The C-Cl bond is activated by fast and effective chloride-ion transfer, the C-F bond is activated by a very slow fluoride-ion transfer, respectively. Thermodynamic and kinetic factors account for the observed selectivity of carbon-halogen versus carbon-hydrogen activation. The cleavage of the C-Cl bond of CH2Cl2 by SO•+ is a rare example of a very effective and selective chloride-ion abstraction by a metal-free, sulphur-centered radical cation.
Selective Activation of C-Cl and C-F Bonds by SO•+ Radical Cations: an Experimental and Computational Study
ROSI, Marzio;
2013
Abstract
The activation of C-halogen bonds of CH2Cl2 and CH2F2 by the SO•+ radical cation is investigated in the gas phase. The C-Cl bond is activated by fast and effective chloride-ion transfer, the C-F bond is activated by a very slow fluoride-ion transfer, respectively. Thermodynamic and kinetic factors account for the observed selectivity of carbon-halogen versus carbon-hydrogen activation. The cleavage of the C-Cl bond of CH2Cl2 by SO•+ is a rare example of a very effective and selective chloride-ion abstraction by a metal-free, sulphur-centered radical cation.File in questo prodotto:
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