PROTON AND ELECTRON TRANSFERS IN O-CENTER-DOT-H-CENTER-DOT-O AND C-CENTER-DOT-H-CENTER-DOT-O HYDROGEN-BRIDGED IONS - THEIR ROLE IN THE DISSOCIATION CHEMISTRY OF IONIZED ACETOL, CH3C(=O)CH2OH-CENTER-DOT+

Low-energy acetol ions CH3C(=O)CH2OH.+, 1, dissociate to CH3C(H)OH+ an d HC=O-. by a double hydrogen transfer (DHT), a common reaction among oxygen-containing radical cations. Recent experimental work has shown that the isotopologue CH3C(=O)CH2OD.+ specifically loses HC=O-. to pro duce CH3C(D)OH+. This finding refutes an earlier postulated attractive mechanism based on the behaviour of 1 in ion-molecule reactions. Usin g ab initio MO calculations (at the CEPA//RHF/DZP level of theory comp lemented with valence bond (VB) methods), a low-energy pathway was tra ced that may explain all of the available experimental observations. I t is shown that the unimolecular chemistry of 1 can be understood in t erms of two proton transfers, taking place in intermediate O . H . O a nd C . H . O bonded hydrogen-bridged radical cations. The two protons originate from the same moiety and a charge transfer complex is theref ore implicated and shown to be involved. These concepts of proton and charge transfer may well be more generally applicable and they do corr ectly predict the unimolecular chemistry of ionized acetoin, CH3C(=O)C H(CH3)OH.+ and related alpha-ketols.