Reactions between small cerium oxide cluster anions and deuterated water were monitored as a function of both water concentration and temperature in order to determine the temperature dependence of the rate constants. Sequential oxidation reactions of the CexOy- (x = 2, 3) suboxide cluster anions were found to exhibit anti-Arrhenius behavior, with activation energies ranging from 0 to -18 kJ mol-1. Direct oxidation of species up to y = x was observed, after which, -OD abstraction and D2O addition reactions were observed. However, the stoichiometric Ce2O4- and Ce3O6- cluster anions also emerge in reactions between D2O and the respective precursors, Ce2O3D- and Ce3O5D2-. Ce2O4- and Ce3O6- product intensities diminish relative to deuteroxide complex intensities with increasing temperature. The kinetics of these reactions are compared to the kinetics of the previously studied MoxOy- and WxOy- reactions with water, and the possible implications for the reaction mechanisms are discussed.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry