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Gas‐Phase Reactions of Cationic Vanadium‐Phosphorus Oxide Clusters with C 2 H x ( x= 4, 6): A DFT‐Based Analysis of Reactivity Patterns
Author(s) -
Dietl Nicolas,
Zhang Xinhao,
van der Linde Christian,
Beyer Martin K.,
Schlangen Maria,
Schwarz Helmut
Publication year - 2013
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.201203050
Subject(s) - heteronuclear molecule , chemistry , vanadium , reactivity (psychology) , vanadium oxide , dehydrogenation , homolysis , inorganic chemistry , cationic polymerization , vanadium carbide , cluster (spacecraft) , crystallography , photochemistry , molecule , catalysis , organic chemistry , radical , medicine , alternative medicine , pathology , computer science , programming language
The reactivities of the adamantane‐like heteronuclear vanadium‐phosphorus oxygen cluster ions [V x P 4− x O 10 ] .+ ( x =0, 2–4) towards hydrocarbons strongly depend on the V/P ratio of the clusters. Possible mechanisms for the gas‐phase reactions of these heteronuclear cations with ethene and ethane have been elucidated by means of DFT‐based calculations; homolytic CH bond activation constitutes the initial step, and for all systems the PO . unit of the clusters serves as the reactive site. More complex oxidation processes, such as oxygen‐atom transfer to, or oxidative dehydrogenation of the hydrocarbons require the presence of a vanadium atom to provide the electronic prerequisites which are necessary to bring about the 2e − reduction of the cationic clusters.