The gas-phase reactivity of ionized nitrile sulfides, R-C[triple bond]N(+)-S*, towards neutral pyridine was studied both experimentally (six sector hybrid mass spectrometer) and theoretically (density functional theory and Møller-Plesset ab initio calculations). An ionized sulfur atom transfer and a cycloaddition process respectively yielding ionized pyridine N-thioxide and a thiazolopyridinium cation were observed. Whereas the very efficient S*+ transfer reaction probably involves the intermediacy of several ion-molecule complexes, the thiazolopyridinium ion formation is likely to be initiated by an electrophilic attack of the R-C[triple bond]N(+)-S* ion on the nitrogen atom of pyridine; the resulting intermediate then undergo an intramolecular substitution of an alpha-hydrogen atom by the sulfur atom.

中文翻译：

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电离的腈基硫化物与吡啶之间气相相互作用的实验和理论研究。

分别通过实验（六扇区混合质谱仪）和理论上（密度泛函理论和Møller-Plesset从头算）研究了离子化的硫化腈RC [三键] N（+）-S *对中性吡啶的气相反应性）。观察到分别产生离子化的吡啶N-硫氧化物和噻唑并吡啶鎓阳离子的离子化硫原子转移和环加成过程。尽管非常有效的S * +转移反应可能涉及几种离子-分子配合物的中间产物，但噻唑并吡啶鎓离子的形成很可能是由R​​C [三键] N（+）-S *离子对化合物的亲电子攻击引发的。吡啶的氮原子；所得的中间体然后被硫原子进行分子内的α-氢原子取代。