The chemistry of solvated distonic ions: Preparation, isomerization, and fragmentation

It has been shown that solvated distonic ions can be prepared by selected c ollision-induced radical removal from the proton-bound dimer of appropriate molecules. The alpha- and beta-distonic ethanol ions solvated by methanol or ethanol, [CH3. CHOH2+/ROH] and [(CH2CH2OH2+)-C-./ROH] (ROH = CH3OH and C 2H5OH), have been prepared by selected loss of a designated radical from th e proton-bound dimer of labeled alcohols, and their reactions studied in th e metastable ion time frame. It is found that isomerization of the alpha-di stonic ion to its conventional structure can be catalyzed by both methanol and ethanol, such that the energy barrier to this process is reduced to 25 +/- 2 kcal mol(-1), lower than that in the: uncatalyzed reaction by 10 kcal mol(-1) The beta-distonic ions do not isomerize to either the alpha-form o r the conventional form when solvated by the alcohol molecule, and their fr agmentation is dominated by water loss, similar to the isolated ion.