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Main Title: Direct Identification of Acetaldehyde Formation and Characterization of the Active Site in the [VPO4].+/C2H4 Couple by Gas‐Phase Vibrational Spectroscopy
Author(s): Li, Ya-Ke
Debnath, Sreekanta
Schlangen, Maria
Schöllkopf, Wieland
Asmis, Knut R.
Schwarz, Helmut
Type: Article
Language Code: en
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.
Issue Date: 8-Nov-2019
Date Available: 13-Feb-2020
DDC Class: 540 Chemie und zugeordnete Wissenschaften
Subject(s): active site
cryogenic ion trap
heteronuclear oxide clusters
infrared photodissociation spectroscopy
olefin oxidation
Sponsor/Funder: DFG, 390540038, EXC 2008: UniSysCat
DFG, 234149247, SFB 1109: Molekulare Einblicke in Metalloxid-Wasser-Systeme: Strukturelle Evolution, Grenzflächen und Auflösung
TU Berlin, Open-Access-Mittel - 2019
Journal Title: Angewandte Chemie International Edition
Publisher: Wiley
Publisher Place: Weinheim
Volume: 58
Issue: 52
Publisher DOI: 10.1002/anie.201911040
Page Start: 18868
Page End: 18872
EISSN: 1521-3773
ISSN: 1433-7851
Appears in Collections:FG Physikalisch-Organische Chemie » Publications

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