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The Competitive O–H versus C–H Bond Activation of Ethanol and Methanol by VO2+ in Gas Phase: A DFT Study

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posted on 2013-06-20, 00:00 authored by Lianming Zhao, Min Tan, Juan Chen, Qiuyue Ding, Xiaoqing Lu, Yuhua Chi, Guangwu Yang, Wenyue Guo, Qingtao Fu
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(Cβ–H) < ΔE(Cα–H) ≈ ΔE(O–H). Loss of methyl and glycol occurs respectively via O–H and Cβ–H activation, while acetaldehyde elimination proceeds through two comparable O–H and Cα–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 Cα–H activation but also forms VO2(C2H4)+ via Cβ–H activation. The major product of ethylene is formed via both O–H and Cβ–H activation for yielding VO­(OH)2+ and VO2(H2O)+. In the methanol reaction, both initial O–H and Cα–H activation accounts for formaldehyde and water elimination, but the former pathway is preferred.

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