Journal of the American Chemical Society, Vol.122, No.23, 5597-5602, 2000
The chemistry of solvated distonic ions: Preparation, isomerization, and fragmentation
It has been shown that solvated distonic ions can be prepared by selected collision-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 C2H5OH), have been prepared by selected loss of a designated radical from the proton-bound dimer of labeled alcohols, and their reactions studied in the metastable ion time frame. It is found that isomerization of the alpha-distonic 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 or the conventional form when solvated by the alcohol molecule, and their fragmentation is dominated by water loss, similar to the isolated ion.