title: Propene oxidation on V4O11- cluster: reaction dynamics to acrolein.
abstract: Oxidation dynamics of propene (CH(3)CH=CH(2)) to acrolein (CH(2)=CHCHO) on the anionic vanadium oxide cluster V(4)O(11)(-) is investigated with the first-principle density functional calculations, providing an interpretation to V(4)O(11)(-) + propene --> V(4)O(10)H(2)(-) + C(3)H(6)O observed in the photochemical reactions (Li, S.; Mirabal, A.; Demuth, J.; Wöste, L.; Siebert, T. J. Am. Chem. Soc. 2008, 130, 16832). The complicated energy surface of the reaction between V(4)O(11)(-) and propene is explored, and the stepwise dynamic processes for propene to acrolein are proposed. Initially, propene is captured by V(4)O(11)(-) with a hydrogen bond CH (methyl group in propene)...O (dioxo group in V(4)O(11)(-)), then undergoes dehydrogenation along this hydrogen bond to form a pi-allyl radical. After the redehydrogenation of the pi-allyl and oxygen transfer from the vanadium oxide cluster, acrolein is eventually produced together with four isomers of V(4)O(10)H(2)(-) in the different reaction paths. During this process, the negative charge is found to transfer between the hydrocarbon and the vanadium oxide moieties.
authors.affiliation: Hefei National Laboratory for Physical Sciences at the Microscale, Department of Chemical Physics, University of Science and Technology of China, Hefei, Anhui 230026, China.
authors.forename: Hai-Bei
authors.initials: HB
authors.lastname: Li
authors.forename: Shan Xi
authors.initials: SX
authors.lastname: Tian
authors.forename: Jinlong
authors.initials: J
authors.lastname: Yang