Premium
Gas‐Phase Dehydrogenation of Methanol with Mononuclear Vanadium‐Oxide Cations
Author(s) -
Engeser Marianne,
Schröder Detlef,
Schwarz Helmut
Publication year - 2005
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200401352
Subject(s) - dehydrogenation , chemistry , methanol , vanadium , inorganic chemistry , metal , oxidation state , vanadium oxide , oxide , hydroxide , mass spectrometry , propene , reactivity (psychology) , catalysis , organic chemistry , medicine , alternative medicine , chromatography , pathology
The reactions of methanol with mass‐selected V + , VOH + , VO + , and VO 2 + 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 VOCH 3 + . In contrast, atomic V + is oxidized and the high‐valent dioxide cation VO 2 + 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.