Dehydration and Dehydrogenation of Alcohols with Mononuclear Cationic Vanadium Oxides in the Gas Phase and Energetics of VO<i>_n</i>H^0/+ (<i>n</i> = 2, 3)

Abstract The ion/molecule reactions of selected alcohols with the vanadium oxide cations VO + and VO 2 + are studied by Fourier‐transform ion‐cyclotron resonance (FT‐ICR) mass spectrometry. Dehydrogenation is the dominating reaction pathway for methanol and allyl alcohols. With larger or less unsaturated alcohols, dehydration and carbocation formations prevail. While the valence in VO + remains unchanged during alcohol dehydrogenation, VO 2 + is reduced to V III . Thermochemical data for VO 2 H 0/+ , VO 3 H and VO 3 H 2 + are derived by means of ICR bracketing. The experimental results are further complemented by ab initio calculations using density functional theory. (© Wiley‐VCH Verlag GmbH &amp; Co. KGaA, 69451 Weinheim, Germany, 2007)