THE LONG-LIVED RADICAL CATIONS OF SIMPLE CARBON ESTERS ISOMERIZE TO THE LOWEST-ENERGY STRUCTURE

The structures of the low-energy, long-lived radical cations of simple gaseous carbon esters were investigated using bimolecular reactions i n a dual-cell FT/ICR mass spectrometer. The molecular ions of dimethyl carbonate, methyl and ethyl formate, methyl and ethyl acetate, and me thyl and ethyl propionate were generated by electron impact or thermon eutral charge exchange. Reference ions with the enol and the expected distonic structures (spatially separated odd spin and charge site) wer e formed by electron impact on suitable neutral precursors or by ion-m olecule reactions using distonic reactant ions. Ionized gamma-butyrola ctone and ionized delta-valerolactone were chosen as models for conven tional ester radical cations. The experimental results demonstrate tha t the lactone ions indeed are stable toward isomerization. The neutral reagents cyclohexanone, triethylamine, and 2-propanol-d(8) proved to be useful when differentiating reference ions with different structure s: (1) Cyclohexanone reacts by charge exchange with the conventional e ster radical cations while enol and distonic ions react by proton tran sfer. (2) Triethylamine reacts with the distonic ions by proton transf er while charge exchange dominates for the enol ions and the conventio nal radical cations. (3) Conventional ester radical cations abstract a deuterium atom from 2-propanol-d(8), while distonic ions and enol ion s react by H/D exchange. Some enol ions also abstract a deuterium atom from this reagent. Comparison of the reactions of the reference ions to those of the ester molecular ions demonstrates unambigously that th e long-lived ionized carbonates and formates have a distonic structure , while the acetate and propionate radical cations have an enol struct ure.