| Summary: | The gas-phase reactivity of vanadium-containing dianions, NaV<sub>3</sub>O<sub>9</sub><sup>2−</sup> and its hydrated form H<sub>2</sub>NaV<sub>3</sub>O<sub>10</sub><sup>2−</sup>, 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 SO<sub>2</sub> molecules to the NaV<sub>3</sub>O<sub>9</sub><sup>2−</sup> dianion leads to the breakage of the stable V<sub>3</sub>O<sub>9</sub> backbone, resulting in a charge separation process with the formation of new V-O and S-O bonds. On the contrary, the H<sub>2</sub>NaV<sub>3</sub>O<sub>10</sub><sup>2−</sup> hydroxide species reacts with SO<sub>2</sub>, promoting regioselective hydrolysis and bond-forming processes, the latter similar to that observed for the NaV<sub>3</sub>O<sub>9</sub><sup>2−</sup> reactant anion. Kinetic analysis shows that these reactions are fast and efficient with rate constants of the 10<sup>−9</sup> (±30) cm<sup>3</sup> s<sup>−1</sup> molecule<sup>−1</sup> order of magnitude.
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