title: The competitive O-H versus C-H bond activation of ethanol and methanol by VO2(+) in gas phase: a DFT study.
abstract: The activation of ethanol and methanol by VO2(+) in gas phase has been theoretically investigated by using density functional theory (DFT). For the VO2(+)/ethanol system, the activation energy (ΔE) is found to follow the order of ΔE(C(β)-H) < ΔE(C(α)-H) ≈ ΔE(O-H). Loss of methyl and glycol occurs respectively via O-H and C(β)-H activation, while acetaldehyde elimination proceeds through two comparable O-H and C(α)-H activations yielding both VO(H2O)(+) and V(OH)2(+). Loss of water not only gives rise to VO(CH3CHO)(+) via both O-H and C(α)-H activation but also forms VO2(C2H4)(+) via C(β)-H activation. The major product of ethylene is formed via both O-H and C(β)-H activation for yielding VO(OH)2(+) and VO2(H2O)(+). In the methanol reaction, both initial O-H and C(α)-H activation accounts for formaldehyde and water elimination, but the former pathway is preferred.
authors.affiliation: College of Science, China University of Petroleum , Qingdao, Shandong 266580, P.R. China.
authors.forename: Lianming
authors.initials: L
authors.lastname: Zhao
authors.forename: Min
authors.initials: M
authors.lastname: Tan
authors.forename: Juan
authors.initials: J
authors.lastname: Chen
authors.forename: Qiuyue
authors.initials: Q
authors.lastname: Ding
authors.forename: Xiaoqing
authors.initials: X
authors.lastname: Lu
authors.forename: Yuhua
authors.initials: Y
authors.lastname: Chi
authors.forename: Guangwu
authors.initials: G
authors.lastname: Yang
authors.forename: Wenyue
authors.initials: W
authors.lastname: Guo
authors.forename: Qingtao
authors.initials: Q
authors.lastname: Fu