On the Gas-Phase Co+-Mediated Oxidation of Ethane by N2O: A Mechanistic Study

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• 作者：Lianming Zhao ; Xiaoqing Lu ; Yuanyuan Li ; Juan Chen ; Wenyue Guo
• 刊名：The Journal of Physical Chemistry A
• 出版年：2012
• 出版时间：March 29, 2012
• 年：2012
• 卷：116
• 期：12
• 页码：3282-3289
• 全文大小：431K
• 年卷期：v.116,no.12(March 29, 2012)
• ISSN：1520-5215

文摘

The potential energy surface (PES) corresponding to the Co⁺-mediated oxidation of ethane by N₂O has been investigated by using density functional theory (DFT). After initial N₂O reduction by Co⁺ to CoO⁺, ethane oxidation by the nascent oxide involves C鈥揌 activation followed by two possible pathways, i.e., C鈥揙 coupling accounting for ethanol, Co⁺-mediated 尾鈥揌 shift giving the energetically favorable product of CoC₂H₄⁺ + H₂O, with minor CoOH₂⁺ + C₂H₄. CoC₂H₄⁺ could react with another N₂O to yield (C₂H₄)Co⁺O, which could subsequently undergo a cyclization mechanism accounting for acetaldehyde and oxirane and/or a direct H-abstraction mechansim for ethenol. Loss of oxirane and ethenol is hampered by respective endothermicity and high kinetics barrier, whereas acetaldehyde elimination is much energetically favorable. CoOH₂⁺ could facilely react with N₂O to form OCoOH₂⁺, rather than Co(OH)₂⁺ or CoO⁺.