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Selective Activation of CCl and CF Bonds by SO .+ Radical Cations: An Experimental and Computational Study
Author(s) -
de Petris Giulia,
Troiani Anna,
Rosi Marzio,
Angelini Giancarlo,
Ursini Ornella
Publication year - 2013
Publication title -
chempluschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.801
H-Index - 61
ISSN - 2192-6506
DOI - 10.1002/cplu.201300162
Subject(s) - chemistry , halogen , chloride , fluoride , bond cleavage , ion , inorganic chemistry , sulfur , halogen bond , radical ion , hydrogen bond , photochemistry , molecule , catalysis , organic chemistry , alkyl
The activation of C–halogen bonds by the SO . + radical cation is investigated in the gas phase. The CCl bond of CH 2 Cl 2 is activated by fast and effective chloride‐ion transfer, whereas the CF bond of CH 2 F 2 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 CCl bond of CH 2 Cl 2 by SO . + is a rare example of a very effective and selective chloride‐ion abstraction by a metal‐free, sulfur‐centred radical cation.