9407080 Grabowski Univ. of Pittsburgh The mechanisms of prototypical ionic gas-phase reactions will be studied and key and/or unusual reactive intermediates will be characterized by gas-phase ion-molecule techniques. The proposed work has two major thrusts, both of which focus on the chemistry of gas-phase anions. The first part will be directed to bimolecular substitution (SN2) reactions at non-carbon first row elements. For example, in this category, SN2 reactions on the oxygen atom in peroxides will be studied. In addition, substitution reactions on nitrogen, fluorine, and chlorine will be pursued. The second part will be directed to a study of distonic radical anions. These newly discovered species have the radical and anionic sites separated on different atoms in the molecule. A number of new synthetic routes to distonic radical anions will be developed and the reactivity of these species will be investigated. This grant from the Organic Dynamics Program supports the work of Professor Joseph J. Grabowski at the University of Pittsburgh. The detailed steps (or mechanisms) of ionic reactions in the gas-phase will be studied by specialized techniques. These reactions can be compared to those carried out in solution in order to determine the effect of solvent, which has a profound effect on the reaction. The reaction of an anionic species at oxygen, nitrogen, fluorine, and chlorine atoms in molecules will be investigated. In addition, the synthesis and reactions of distonic anions, a new type of species, will be pursued. These novel species have one unit of negative charge and one non-bonded electron on different atoms.
