Theoretical Studies on the Gas-phase Reaction of Methyl Formate with Anions

摘要

The gas-phase reactions of methyl formate with anions, -NH2, -OH, -CH2CN, are studied theoretically using the AM1 method. Stationary points are located by the reaction coordinate method, refined by the gradient norm minimization and characterized by the determination of Hessian matrix. Potential energy profiles and the stationary point structures are presented for all conceivable processes. Four reaction paths are found to be possible: formyl proton and methyl proton abstractions, carbonyl addition, and SN2 process. For the most basic anion -NH2 the proton abstraction path is favored, while in other case, OH and -CH2CN, the carbonyl addition paths are favored. In all cases the SN2 process is the most exothermic, but due to the relatively high activation barrier the process can be ruled out.