Regioselective Bond-Forming and Hydrolysis Reactions of Doubly Charged Vanadium Oxide Anions in the Gas Phase

Abstract

The gas-phase reactivity of vanadium-containing dianions, NaV3O92− and its hydrated form H2NaV3O102−, were probed towards sulphur dioxide at room temperature by ion-molecule reaction (IMR) experiments in the collision cell of an ion trap mass spectrometer. The sequential addition of two SO2 molecules to the NaV3O92− dianion leads to the breakage of the stable V3O9 backbone, resulting in a charge separation process with the formation of new V-O and S-O bonds. On the contrary, the H2NaV3O102− hydroxide species reacts with SO2, promoting regioselective hydrolysis and bond-forming processes, the latter similar to that observed for the NaV3O92− reactant anion. Kinetic analysis shows that these reactions are fast and efficient with rate constants of the 10−9 (±30) cm3 s−1 molecule−1 order of magnitude.