title: Ce(x)O(y)⁻ (x = 2-3) + D₂O reactions: stoichiometric cluster formation from deuteroxide decomposition and anti-Arrhenius behavior.
abstract: 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 Ce(x)O(y)⁻ (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 Mo(x)O(y)⁻ and W(x)O(y)⁻ reactions with water, and the possible implications for the reaction mechanisms are discussed.
authors.affiliation: Department of Chemistry, Indiana University , 800 East Kirkwood Avenue, Bloomington, Indiana 47405, United States.
authors.forename: Jeremy A
authors.initials: JA
authors.lastname: Felton
authors.forename: Manisha
authors.initials: M
authors.lastname: Ray
authors.forename: Sarah E
authors.initials: SE
authors.lastname: Waller
authors.forename: Jared O
authors.initials: JO
authors.lastname: Kafader
authors.forename: Caroline Chick
authors.initials: CC
authors.lastname: Jarrold