Selective Activation of CCl and CF Bonds by SO.+ Radical Cations: An Experimental and Computational Study. Issue 9 (16th July 2013)

• Record Type: Journal Article
• Authors: de Petris, Giulia; Troiani, Anna; Rosi, Marzio; Angelini, Giancarlo; Ursini, Ornella
• Is Part Of: ChemPlusChem. Volume 78:Issue 9(2013:Sep.)
• Page Start: 1065
• Page End: 1072
• Publication Date: 2013-07-16
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1002/cplu.201300162
• Languages: English
• ISSNs: 2192-6506

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>The activation of C–halogen bonds by the SO<bold>^.</bold>⁺ 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 SO<bold>^.</bold>⁺ is a rare example of a very effective and selective chloride‐ion abstraction by a metal‐free, sulfur‐centred radical cation.</p> </abstract>