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首页> 外文期刊>Chemistry: A European journal >Gas-Phase Reactions of Nitronium Ions with Acetylene and Ethylene: An Experimental and Theoretical Study
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Gas-Phase Reactions of Nitronium Ions with Acetylene and Ethylene: An Experimental and Theoretical Study

机译：氮离子与乙炔和乙烯的气相反应：实验和理论研究

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摘要

A comparative study of the gas-phase reactions of NO_2~+ with acetylene and ethylene was performed by using FT-ICR, MIKE, CAD, and N_fR/CA mass spectrometric techniques, in conjunction with ab initio calculations at the MP2/6-31+G~* level of theory. Both reactions proceed according to the same mechanism, that is, 1, 3-dipolar cycloaddition, but yield products of different stability. The C_2H_2NO_2~+ adduct from acetylene has an aromatic character and hence is highly stabilized with respect to the C_2H_4NO_2~+ adduct from ethylene. Both cycloadducts tend to isomerize into O-nitroso derivatives, that is, nitrosated ketene and nitrosated acetalkehyde, which represent the thermodynamically most stable products from the addition of NO_2~+ to acetylene and ethylene, Both cycloadducts tend to isomerize into O-nitroso derivatives, that is, nitrosated ketene and nitrosated acetalkehyde, which represent the thermodynamically most stable products from the addition of NO_2~+ to acetylene and ethylene, respectively. As prototypal examples of the reactivity of free nitronium ions with most simple #pi# systems, the reactions investigated are useful starting points to model the mechanism of aromatic nitration.
机译：利用FT-ICR，MIKE，CAD和N_fR / CA质谱技术，结合从头算在MP2 / 6-31处，对NO_2〜+与乙炔和乙烯的气相反应进行了比较研究。 + G〜*理论水平。两种反应均按照相同的机理进行，即1，3-偶极环加成反应，但生成的产物具有不同的稳定性。来自乙炔的C_2H_2NO_2〜+加合物具有芳香性，因此相对于来自乙烯的C_2H_4NO_2〜+加合物高度稳定。两种环加合物都倾向于异构化为O-亚硝基衍生物，即亚硝化的乙烯酮和亚硝化的乙醛，它们代表了从NO_2〜+到乙炔和乙烯中的热力学最稳定的产物。两种环加合物都倾向于异构化为O-亚硝基的衍生物，即亚硝化的乙烯酮和亚硝化的乙醛，分别代表了在乙炔和乙烯中添加NO_2〜+所获得的热力学最稳定的产物。作为游离硝基离子与最简单的＃pi＃系统的反应性的原型示例，研究的反应是建立芳族硝化机理模型的有用起点。

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