Gas-phase reactions of anions with halogenated methanes at 297 ± 2 K

Abstract

The rate constants for a number of exothermic displacement (SN2) reactions of the type X− + CH3Y → Y− + CH3X where X− = H−, O−, C−, F−, S−, Cl−, OH−, C2−, CN−, SH−, S2−, C2H−, NH2−, NO2−, CHF−, CH2Cl−, CH2Br−, CH3O−, CH3S−, and CH3NH− and Y = F, Cl, and Br, have been measured in the gas phase at 297 ± 2 K using the flowing after-glow technique. These gas-phase measurements provided an opportunity to determine the intrinsic nucleophilic reactivity of 'nude' anions and hence to assess the role of solvation in the kinetics of SN2 reactions proceeding in solution. Comparisons of the experimental rate constants with rate constants calculated using classical theories of capture indicate that several displacement reactions may possess large intrinsic energies of activation, [Formula: see text]. Correlations were found between apparent activation energies and the heats of reaction. These correlations provided a convenient classification of the various anion nucleophiles. Displacement was observed to compete with proton transfer in reactions involving nucleophiles of high intrinsic basicity and with hydrogen atom transfer and H2+ transfer in the reactions of the O− radical anion.