Reactions of α-Nucleophiles with Alkyl Chlorides: Competition between SN2 and E2 Mechanisms and the Gas-Phase α-Effect

Reaction rate constants and deuterium kinetic isotope effects for the reactions of BrOwith RCl (R ) methyl, ethyl, isopropyl, and tert-butyl) were measured using a tandem flowing afterglow-selected ion flow tube instrument. These results provide qualitative insight into the competition between two classical organic mechanisms, nucleophilic substitution (SN2) and base-induced elimination (E2). As the extent of substitution in the neutral reactants increases, the kinetic isotope effects become increasingly more normal, consistent with the gradual onset of the E2 channel. These results are in excellent agreement with previously reported trends for the analogous reactions of ClOwith RCl. [Villano et al. J. Am. Chem. Soc. 2006, 128, 728.] However, the reactions of BrOand ClOwith methyl chloride, ethyl chloride, and isopropyl chloride were found to occur by an additional reaction pathway, which has not previously been reported. This reaction likely proceeds initially through a traditional SN2 transition state, followed by an elimination step in the SN2 product ion-dipole complex. Furthermore, the controversial R-nucleophilic character of these two anions and of the HO2 anion is examined. No enhanced reactivity is displayed. These results suggest that the R-effect is not due to an intrinsic property of the anion but instead due to a solvent effect.