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Selective Activation of CCl and CF Bonds by SO.+ Radical Cations: An Experimental and Computational Study.
de Petris, Giulia; Troiani, Anna; Rosi, Marzio; Angelini, Giancarlo; Ursini, Ornella.
Afiliación
  • de Petris G; Dipartimento di Chimica e Tecnologie del Farmaco, "Sapienza" University of Rome, P.le Aldo Moro 5, 00185 Roma (Italy), Fax: (+39) 06-49913604.
  • Troiani A; Dipartimento di Chimica e Tecnologie del Farmaco, "Sapienza" University of Rome, P.le Aldo Moro 5, 00185 Roma (Italy), Fax: (+39) 06-49913604.
  • Rosi M; Dipartimento di Ingegneria Civile e Ambientale, Università di Perugia and ISTM-CNR, Via Duranti 93, 06125 Perugia (Italy).
  • Angelini G; Istituto di Metodologie Chimiche, Area della Ricerca di Roma del CNR, CP 10, 00016 Monterotondo Stazione (RM) (Italy).
  • Ursini O; Istituto di Metodologie Chimiche, Area della Ricerca di Roma del CNR, CP 10, 00016 Monterotondo Stazione (RM) (Italy).
Chempluschem ; 78(9): 1065-1072, 2013 Sep.
Article en En | MEDLINE | ID: mdl-31986735
The activation of C-halogen bonds by the SO. + radical cation is investigated in the gas phase. The CCl bond of CH2 Cl2 is activated by fast and effective chloride-ion transfer, whereas the CF bond of CH2 F2 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 CH2 Cl2 by SO. + is a rare example of a very effective and selective chloride-ion abstraction by a metal-free, sulfur-centred radical cation.
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: Chempluschem Año: 2013 Tipo del documento: Article Pais de publicación: Alemania
Texto completo
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Imprimir
XML
PubMed Links
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: Chempluschem Año: 2013 Tipo del documento: Article Pais de publicación: Alemania