화학공학소재연구정보센터
Journal of the American Chemical Society, Vol.122, No.15, 3695-3700, 2000
Selected radical removal from proton-bound dimers. A strategy for studying solvated distonic ions
The formal ion-molecule pairs [(CH2OH2+)-C-./CH3OH] and [(CH2OH2+)-C-./H2O] were generated by selected radical loss from appropriate proton-bound molecular pairs. The radical loss was activated by keV energy collisions with He in a tandem mass spectrometer, e.g., [CH3CH2OD2+/DOCD3] --> [(CH2OD2+)-C-./CD3OD] + CH3.. The metastable ion dissociations of the above species and their appropriate deuterium-labeled analogues were recorded. These were the losses of a methyl radical, water, and C,H-3,O from the former pair and losses of water and (CH2OH)-C-. from the latter. The observations showed that the interconversions of ionized methanol and its distonic isomer were catalyzed by the neutral partner molecule. With H2O as catalyst, all H atoms are involved in the arrangements that precede metastable dissociations, whereas with methanol as catalyst, its H atoms retain their positional identity. The relationship between these metastable ion systems and the higher energy species involved in bimolecular reaction is discussed in terms of proton-transport catalysis.