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.

SUBMITTER: Dietl N 

PROVIDER: S-EPMC3743165 | biostudies-literature | 2013 Feb

REPOSITORIES: biostudies-literature