title: Gas-phase reactions of cationic vanadium-phosphorus oxide clusters with C2H(x) (x=4, 6): a DFT-based analysis of reactivity patterns.
abstract: 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 C-H bond activation constitutes the initial step, and for all systems the P-O(.) 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.
authors: Institut für Chemie, Technische Universität Berlin, Straße des 17. Juni 135, 10623 Berlin, Germany.
authors: Nicolas
authors: N
authors: Dietl
authors: Xinhao
authors: X
authors: Zhang
authors: Christian
authors: C
authors: van der Linde
authors: Martin K
authors: MK
authors: Beyer
authors: Maria
authors: M
authors: Schlangen
authors: Helmut
authors: H
authors: Schwarz
mesh_terms: D002412:Cations / Q000737:chemistry*; D003198:Computer Simulation; D015394:Molecular Structure; D010084:Oxidation-Reduction; D010758:Phosphorus / Q000737:chemistry*; D014639:Vanadium / Q000737:chemistry*
chemical_list: D002412:Cations; D014639:Vanadium; D010758:Phosphorus