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Direct Identification of Acetaldehyde Formation and Characterization of the Active Site in the [VPO 4 ] .+ /C 2 H 4 Couple by Gas‐Phase Vibrational Spectroscopy
Author(s) -
Li YaKe,
Debnath Sreekanta,
Schlangen Maria,
Schöllkopf Wieland,
Asmis Knut R.,
Schwarz Helmut
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201911040
Subject(s) - heteronuclear molecule , chemistry , context (archaeology) , molecule , infrared spectroscopy , crystallography , acetaldehyde , intramolecular force , stereochemistry , organic chemistry , paleontology , biology , ethanol
The gas‐phase reaction of the heteronuclear oxide cluster [VPO 4 ] .+ with C 2 H 4 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 C 2 H 4 →CH 3 CHO conversion. Interestingly, in the course of the reaction, the emerging CH 3 CHO product undergoes a rather complex intramolecular migration, coordinating eventually to the vanadium center prior to its liberation. Moreover, the spectroscopic structural characterization of neutral C 2 H 4 O deserves special mentioning as in most, if not all, ion/molecule reactions, the neutral product is usually only indirectly identified.