title: Structure and chemistry of the heteronuclear oxo-cluster [VPO4]•+: a model system for the gas-phase oxidation of small hydrocarbons.
abstract: The heteronuclear oxo-cluster [VPO4](•+) is generated via electrospray ionization and investigated with respect to both its electronic structure as well as its gas-phase reactivity toward small hydrocarbons, thus permitting a comparison to the well-known vanadium-oxide cation [V2O4](•+). As described in previous studies, the latter oxide exhibits no or just minor reactivity toward small hydrocarbons, such as CH4, C2H6, C3H8, n-C4H10, and C2H4, while substitution of one vanadium by a phosphorus atom yields the reactive [VPO4](•+) ion; the latter brings about oxidative dehydrogenation (ODH) of saturated hydrocarbons, e.g., propane and butane as well as oxygen-atom transfer (OAT) to unsaturated hydrocarbons, e.g. ethene, at thermal conditions. Further, the gas-phase structure of [VPO4](•+) is determined by IR photodissociation spectroscopy and compared to that of [V2O4](•+). DFT calculations help to elucidate the reaction mechanism. The results underline the crucial role of phosphorus in terms of C-H bond activation of hydrocarbons by mixed VPO clusters.
authors: Institut für Chemie, Technische Universität Berlin, Straße des 17. Juni 135, D-10623 Berlin, Germany.
authors: Nicolas
authors: N
authors: Dietl
authors: Torsten
authors: T
authors: Wende
authors: Kai
authors: K
authors: Chen
authors: Ling
authors: L
authors: Jiang
authors: Maria
authors: M
authors: Schlangen
authors: Xinhao
authors: X
authors: Zhang
authors: Knut R
authors: KR
authors: Asmis
authors: Helmut
authors: H
authors: Schwarz
mesh_terms: D002384:Catalysis; D005740:Gases / Q000737:chemistry; D006838:Hydrocarbons / Q000737:chemistry*; D015394:Molecular Structure; D010084:Oxidation-Reduction; D010710:Phosphates / Q000737:chemistry*; D011789:Quantum Theory; D014639:Vanadium / Q000737:chemistry*
chemical_list: D005740:Gases; D006838:Hydrocarbons; D010710:Phosphates; D014639:Vanadium