Using the flowing afterglow-selected ion flow tube technique, we have explored the gas phase ion chemistry of alpha nucleophiles. These ions, such as HOO- that contain lone electron pairs adjacent to the reaction center, were shown to exhibit enhanced reactivity in solution more than 50 years ago. However, the origin of this “alpha effect”, as an intrinsic property or as a solvent effect, is not fully understood. We have experimentally determined the reaction rates constants for the nucleophilic substitution reactions of normal and alpha nucleophiles, and of their microsolvated anions. Computations provide insight into the energetics and structures, including the unexpected finding that the stable form of hydrated hydroperoxide ion is HO-(HOOH) rather than HOO-(HOH). Direct dynamics simulations by Xie and Hase corroborate the experimental results and reveal a new reaction pathway.

Gas phase ion chemistry of alpha nucleophiles

ACS Spring Meeting 2021

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.