Gas-phase dehydrogenation of methanol with mononuclear vanadium-oxide cations

The reactions of methanol with mass-selected V+, VOH+, VO+, and VO2(+) cations are studied by Fourier-transform ion-cyclotron resonance (FT-ICR) mass spectrometry in order to investigate the influence of the formal oxidation state of the metal on the reactivity of vanadium-oxide compounds. Interestingly, the most reactive species is the low-valent hydroxide cation VOH+, for which a formal condensation reaction prevails to afford VOCH3(+). In contrast, atomic V+ is oxidized and the high-valent dioxide cation VO2(+) is reduced by methanol. The dehydrogenation of methanol mediated by VO+ does not involve any change of the metal's oxidation state. For the latter reaction, the experimental results are complemented by a theoretical investigation by using density functional theory.