Abstract Two sulfamoyl azides, H2NS(O)2N3 and MeN(H)S(O)2N3, have been isolated as neat substances and characterized. The solid-state structure of the parent molecule H2NS(O)2N3 has been established with X-ray crystallography. The thermal decomposition of both azides has been studied by combining flash vacuum pyrolysis (FVP, 400 °C) and matrix-isolation IR spectroscopy. In addition to the complete dissociation fragments for H2NS(O)2N3 (SO2, N2, and H2) and MeN(H)S(O)2N3 (SO2, N2, and CH2NH), the retro-ene decomposition products HN3 and N-sulfonylamines HNSO2 and MeNSO2 form, respectively. Alternatively, quantitative yield of both N-sulfonylamines in the gas phase occurs when sulfamoyl chlorides H2NS(O)2Cl and MeN(H)S(O)2Cl are used as the FVP precursors (400 °C). Consistent with these experimental observations, computational studies on the potential energy profiles for the decomposition of the two azides at the CCSD(T)/aug-cc-pVTZ//B3LYP/6-311++G(3df,3pd) level conclusively suggest that the N2-elimination is energetically more favorable than the HN3-elimination through either retro-ene reaction or 1,2-elimination. In contrast, the facile HCl-elimination from sulfamoyl chlorides provides a general method for the gas-phase generation of N-sulfonylamines, which were known as transient reactive intermediates in synthetic chemistry.

中文翻译：

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氨磺酰叠氮化物和氯化物的快速真空热解：瞬态 N-磺胺的简便气相生成

摘要 两种氨磺酰叠氮化物 H2NS(O)2N3 和 MeN(H)S(O)2N3 已被分离为纯物质并进行表征。母体分子 H2NS(O)2N3 的固态结构已通过 X 射线晶体学确定。通过结合快速真空热解 (FVP, 400 °C) 和基质隔离红外光谱，研究了两种叠氮化物的热分解。除了 H2NS(O)2N3（SO2、N2 和 H2）和 MeN(H)S(O)2N3（SO2、N2 和 CH2NH）的完全解离碎片之外，逆烯分解产物 HN3 和 N-磺胺分别形成 HNSO2 和 MeNSO2。或者，当氨磺酰氯 H2NS(O)2Cl 和 MeN(H)S(O)2Cl 用作 FVP 前体 (400 °C) 时，气相中两种 N-磺胺的定量产率就会发生。与这些实验观察一致，在 CCSD(T)/aug-cc-pVTZ//B3LYP/6-311++G(3df,3pd) 水平对两种叠氮化物分解的势能分布的计算研究最终表明 N2 消除是通过逆烯反应或 1,2-消除在能量上比 HN3 消除更有利。相比之下，从氨磺酰氯中轻松消除 HCl 为气相生成 N-磺胺提供了一种通用方法，N-磺胺在合成化学中被称为瞬态反应中间体。