Gas-phase reactions of [VO2(OH)2]- and [V2O5(OH)]- with methanol: Experiment and theory

Abstract

The gas-phase reactivity of the vanadium hydroxides [VO2(OH) 2]- and [V2O5(OH)]- toward methanol was examined using a combination of ion-molecule reactions (IMRs) and collision-induced dissociation (CID) in a quadrupole ion trap mass spectrometer. Isotope-labeling experiments with CD3OH, 13CH3OH, and CH318OH were used to confirm the stoichiometry of ions and the observed sequence of reactions. The experimental data were interpreted with the aid of density functional theory calculations, carried out at the B3LYP/SDD6-311++G* level of theory. While [VO2(OH)2]- is unreactive, [V 2O5(OH)]- undergoes a metathesis reaction to yield [V2O5(OCH3)]-. The DFT calculations reveal that the metathesis rea..