Competition of Proton and Electron Transfers in Gas-Phase Reactions of Hydrogen-Containing Dications CHX2+ (X=F, Cl, Br, I) with Atoms, Nonpolar and Polar Molecules

✍ Scribed by Jana Roithová; Zdenek Herman; Detlef Schröder; Helmut Schwarz

• Publisher: John Wiley and Sons
• Year: 2006
• Tongue: English
• Weight: 167 KB
• Volume: 12
• Category: Article
• ISSN: 0947-6539
• DOI: 10.1002/chem.200500888

✦ Synopsis

Abstract

The competition between proton and electron transfer in reactions of mass‐selected dications CHX^2+^ (X=F, Cl, Br, and I) with rare gas atoms (Ne, Ar, Kr, and Xe) and selected molecular reagents (N~2~, O~2~, CO, H~2~O, and HCl) is studied in the gas phase. In the ion–molecule reactions of CHX^2+^ dications with atoms and nonpolar molecules, it is the energy balance of electron transfer that acts as the decisive factor: when the exothermicity of electron transfer exceeds 2 eV, this process predominates at the expense of bond‐forming proton transfer. In marked contrast, the reactions between these triatomic dications and polar molecules are governed for the benefit of the thermochemically more favored products resulting from proton transfer.