Theoretical Studies on Gas-Phase Reactions of Negative Ions with Alkyl Nitrites

摘要

Gas-Phase reactions of methyl and ethyl nitrites with anionic nucleophiles of SH-, F- and OH- are investigated theoretically at the MP2/6-311+G* level. The SN2 processes are all highly exothermic and proceed with a typ-icaI double-weIl reaction coordinate profile. The elimination reactions of methyl nitrite with SH- and F- are double-well energy surface processes,with stabilizedproduct complexes of NO-...H2S and NO-...HF, pro-ceeding by an E1 cb-like E2 mechanism. The モ-elimination of ethyl nitrite is an E2 type process. The メ-elimi-nation reactions of methyl and ethyl nitrites with OH- have triple-well energy profiles of Elcb pathway with an メ-carbanion intermediate which is stabilized bythe vicinal ncメ-*o-N charge transfer interactions. CompIex-ation ofmethyl carbanion with HF seems to provide a stable intermediate within a triple-well energy profile of El cb channel in the reaction of F- with methyl nitrite.