Gas-phase reactions of cationic molybdenum and tungsten monoxide with ethanol: a combined experimental/computational exercise

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• 作者：Patricio González-Navarrete ; Maria Schlangen ; Helmut Schwarz
• 关键词：Ethanol ; Gas ; phase reactivity ; Molybdenum ; Tungsten ; Dehydration ; Dehydrogenation
• 刊名：Structural Chemistry
• 出版年：2017
• 出版时间：April 2017
• 年：2017
• 卷：28
• 期：2
• 页码：403-413
• 全文大小：
• 刊物类别：Chemistry and Materials Science
• 刊物主题：Computer Applications in Chemistry; Physical Chemistry; Theoretical and Computational Chemistry;
• 出版者：Springer US
• ISSN：1572-9001
• 卷排序：28

文摘

The ion/molecule reactions of molybdenum and tungsten monoxide cations MO+ (M═Mo, W) with ethanol have been studied by Fourier transform ion-cyclotron resonance mass spectrometry (FT-ICR MS) and density functional theory (DFT) calculations. As observed in the previously reported reactions of MO₂+ (M═Mo, W) towards ethanol, the dehydration of ethanol to give rise to the elimination of neutral C₂H₄ constitutes also the dominating reaction channel for the monoxides. Likewise, both systems result in a combined dehydrogenation/dehydration process, thus forming the ionic product MOC₂H₂+; moreover, the tungsten system presents two additional reaction channels: double dehydrogenation of ethanol with concomitant formation of the ionic product WO₂C₂H₂+ and the generation of C₂H₅+ which takes place by OH− transfer from ethanol to the tungsten atom. This combined experimental/computational study of gas-phase ion molecule reactions may shed some new light on the mechanisms that occur in complex catalytic systems.