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Abstract

The gas‐phase reaction of the heteronuclear oxide cluster [VPO₄]^.+ with C₂H₄ is studied under multiple collision conditions at 150 K using cryogenic ion‐trap vibrational spectroscopy combined with electronic structure calculations. The exclusive formation of acetaldehyde is directly identified spectroscopically and discussed in the context of the underlying reaction mechanism. In line with computational predictions it is the terminal P=O and not the V=O unit that provides the oxygen atom in the barrier‐free thermal C₂H₄→CH₃CHO conversion. Interestingly, in the course of the reaction, the emerging CH₃CHO product undergoes a rather complex intramolecular migration, coordinating eventually to the vanadium center prior to its liberation. Moreover, the spectroscopic structural characterization of neutral C₂H₄O deserves special mentioning as in most, if not all, ion/molecule reactions, the neutral product is usually only indirectly identified.