CONSEQUENCES OF CHARGE REVERSAL OF GASEOUS FORMATE AND ACETATE IONS - ACYLOXY IONS

Positive-ion collision-induced decomposition (CID) mass-analyzed ion kinetic energy (MIKE) spectra of formate and acetate anions were compared with the CID MIKE spectra of COOH+, CH2COOH+, and COOCH3+, the likely simple rearrangement products of the formyloxy and acetyloxy cations. The spectra of the charge-reversed ions formed from the carboxylate anions differed from the spectra of the models, and gave fragment ions consistent with no structural rearrangement. The initially formed ion was found to rearrange with no energy barrier to COOR+using MINDO/3; for HCOO+this was duplicated by STO-3G and 4-31G calculations. © 1979, American Chemical Society. All rights reserved.