Selective Activation of C Cl and C F Bonds by SO.+ Radical Cations: An Experimental and Computational Study

The activation of C-halogen bonds by the SOC+ radical cation is investigated in the gas phase. The C-Cl bond of CH2Cl2 is activated by fast and effective chloride-ion transfer, whereas the C-F bond of CH2F2 is activated by a very slow fluoride-ion transfer. In both cases, thermodynamic and kinetic factors account for the type of process and the observed selectivity, that is, carbon-halogen versus carbon-hydrogen activation, mainly owing to the presence of the sulfur atom. The cleavage of the C-Cl bond of CH2Cl2 by SOC+ is a rare example of a very effective and selective chloride-ion abstraction by a metal-free, sulfur-centred radical cation.