Propene oxidation on V4O11- cluster: reaction dynamics to acrolein.
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.
Li
Hai-Bei
HB
Hefei National Laboratory for Physical Sciences at the Microscale, Department of Chemical Physics, University of Science and Technology of China, Hefei, Anhui 230026, China.
Tian
Shan Xi
SX
Yang
Jinlong
J