Nitrogen incorporation in saturated aliphatic C6-C8 hydrocarbons and ethanol in low-pressure nitrogen plasma generated by a hollow cathode discharge ion source
Nitrogen incorporation in saturated aliphatic C6-C8 hydrocarbons and ethanol in low-pressure nitrogen plasma generated by a hollow cathode discharge ion source
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DOI：
10.1002/jms.3765
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发表时间：
2016-06-01
影响因子：
2.3
通讯作者：
Yamabe, Shinichi
中科院分区：
文献类型：
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作者：
Usmanov, Dilshadbek T.;Chen, Lee Chuin;Yamabe, Shinichi
利用Orbitrap质谱仪研究了空心阴极放电离子源产生的28-TorrN(2)等离子体中饱和烃（正己烷、环己烷、正庚烷、正辛烷和异辛烷）的离子/分子反应。结果表明，以[M+14]（+）为主离子（M：样品分子）。精确的质量分析表明，这些离子是由N-3（+）与M反应形成的氮化分子[M+N](+)，通过密度泛函理论计算验证了N-3(+) + M[M+N](+) +N -2的反应。发现N-3（+）从碳氢化合物分子中抽离H原子，形成质子化亚胺以RRCNH2+的形式（即C-H键氮化）。这一结果与NH3的消除是[M+N]（+）质谱比的主要通道这一事实是一致的。也就是说，氮被结合到饱和碳氢化合物的C-H键中。苯和丙酮没有发生氮化反应，这是由密度泛函理论计算得出的稳定的电荷转移配合物benzeneN(3)（+）和acetoneN(3)（+）形成的。版权所有：John Wiley & Sons， Ltd。
Ion/molecule reactions of saturated hydrocarbons (n-hexane, cyclohexane, n-heptane, n-octane and isooctane) in 28-TorrN(2) plasma generated by a hollow cathode discharge ion source were investigated using an Orbitrap mass spectrometer. It was found that the ions with [M+14](+) were observed as the major ions (M: sample molecule). The exact mass analysis revealed that the ions are nitrogenated molecules, [M+N](+) formed by the reactions of N-3(+) with M. The reaction, N-3(+) + M[M+N](+) + N-2, were examined by the density functional theory calculations. It was found that N-3(+) abstracts the H atom from hydrocarbon molecules leading to the formation of protonated imines in the forms of RRCNH2+ (i.e. C-H bond nitrogenation). This result is in accord with the fact that elimination of NH3 is the major channel for MS/MS of [M+N](+). That is, nitrogen is incorporated in the C-H bonds of saturated hydrocarbons. No nitrogenation was observed for benzene and acetone, which was ascribed to the formation of stable charge-transfer complexes benzeneN(3)(+) and acetoneN(3)(+) revealed by density functional theory calculations. Copyright (c) 2016 John Wiley & Sons, Ltd.