The gas-phase reactions of vanadium oxide cluster ions with 1,3-butadiene and the isomers of butene are examined. The correlation between the reaction products and the cluster stoichiometry, oxidation and charge-state are explored by studying the reactivity of 1,3-butadiene (C4H6) and the deuterated 1,3-butadienes C4D6 and 1,1,4,4-C4D4H2 with the clusters cations V3O6+, V3O7+, and V3O8+ and the anions VO2.3-, V2O4-6-, V3O6-9- and V4O10.11-. These studies further our understanding of the reactions of VxOy+ clusters with hydrocarbons, as reported previously [Bell, R. C.; Zemski, K. A.; Kerns, K. P.; Deng, H. T.; Castleman, Jr., A. W. J. Phys. Chem. A 1998, 102, 1733], by examining the reaction of the anions (VxOy-), deuterated butadiene species and the 2-butenes. The reactions of C4D6 and 1,1,4,4-C4D4H2 with the cluster V3O7+ demonstrate pathways for the loss of a single oxygen, oxidative dehydrogenation, and molecular association, as well as other minor products, analogous to the products previously reported for the reactions of these clusters with C4H6. The reactions of V3O7+ with the isomers of butene (1-butene, cis-2-butene and trans-2-butene) display many of the same reaction pathways that are observed for 1,3-butadiene, namely, oxidation of the hydrocarbon, oxidative dehydrogenation, and molecular association. In addition, a major channel representing the dehydrogenation of the alkene and a minor channel for C2-C3 cracking of the alkene, along with other minor products is also observed. The anionic clusters VO2.3-, V2O4.5, V3O6-8-, and V4O10- do not react with either 1,3-butadiene or 1-butene, whereas clusters of higher oxygen content, V2O6-, V3O9-, and V4O11- display a minor reaction channel for the loss of a single oxygen atom, presumably through oxidation of the hydrocarbon and resulting in the cluster VxOy-1-.
All Science Journal Classification (ASJC) codes
- Physical and Theoretical Chemistry