Neutralization–reionization study of the allyloxide anion

The charge-reversal (CR) and neutralization–reionization (NR) mass spectra of the mass-selected allyloxide anion CH2CHCH2O− are reported. Similar to other alkoxide ions, the allyloxide anion shows only small abundances of the survivor cation in the CR and NR spectra. In combination with theoretical studies, the differences between the CR and NR experiments allow to explain why loss of atomic hydrogen corresponds to the major unimolecular decomposition channel of the neutral allyloxy radical. In addition, indirect evidence for an intramolecular rearrangement of the allyloxy radical to a carbon-centered oxiranyl methyl radical is provided. Interestingly, the patterns of the C3HnO+ ions in the NR spectra show similarities to those of a recently reported photoionization study of oxygenated products formed upon interaction of V4O11− ions with propene. By extrapolation of our findings, we suggest that the reactions of the vanadium-oxide cluster anion V4O11− are initiated by allylic C–H bond activation of propene followed by oxygenation of the hydrocarbon fragment.

Graphical abstractThe pattern of C3HnO+ ions formed upon neutralization–reionization of CH2CHCH2O− show similarities to the photoionized oxygenates formed from V4O11− and propene, suggesting occurrence of initial allylic C–H bond activation followed by oxygenation.Figure optionsDownload full-size imageDownload high-quality image (134 K)Download as PowerPoint slide