College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China.
Department of Chemistry, Graduate School of Science, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8526, Japan.
Molecules. 2018 Dec 13;23(12):3312. doi: 10.3390/molecules23123312.
Chloro- and dichloro-methylsulfonyl nitrenes, CH₂ClS(O)₂N and CHCl₂S(O)₂N, have been generated from UV laser photolysis (193 and 266 nm) of the corresponding sulfonyl azides CH₂ClS(O)₂N₃ and CHCl₂S(O)₂N₃, respectively. Both nitrenes have been characterized with matrix-isolation IR and EPR spectroscopy in solid N₂ (10 K) and glassy toluene (5 K) matrices. Triplet ground-state multiplicity of CH₂ClS(O)₂N (|/| = 1.57 cm and |/| = 0.0026 cm) and CHCl₂S(O)₂N (|/| = 1.56 cm and |/| = 0.0042 cm) has been confirmed. In addition, dichloromethylnitrene CHCl₂N (|/| = 1.57 cm and |/| = 0 cm), formed from SO₂-elimination in CHCl₂S(O)₂N, has also been identified for the first time. Upon UV light irradiation (365 nm), the two sulfonyl nitrenes R⁻S(O)₂N (R = CH₂Cl and CHCl₂) undergo concomitant 1,2-R shift to -sulfonlyamines R⁻NSO₂ and 1,2-oxygen shift to -nitroso compounds R⁻S(O)NO, respectively. The identification of these new species with IR spectroscopy is supported by N labeling experiments and quantum chemical calculations at the B3LYP/6-311++G(3df,3pd) level. In contrast, the thermally-generated sulfonyl nitrenes CH₂ClS(O)₂N (600 K) and CHCl₂S(O)₂N (700 K) dissociate completely in the gas phase, and in both cases, HCN, SO₂, HCl, HNSO, and CO form. Additionally, ClCN, OCCl₂, HNSO₂, •NSO₂, and the atmospherically relevant radical •CHCl₂ are also identified among the fragmentation products of CHCl₂S(O)₂N. The underlying mechanisms for the rearrangement and decomposition of CH₂ClS(O)₂N and CHCl₂S(O)₂N are discussed based on the experimentally-observed products and the calculated potential energy profile.
氯代和二氯代甲基亚磺酰基氮烯，CH₂ClS(O)₂N 和 CHCl₂S(O)₂N，分别由相应的磺酰叠氮化物 CH₂ClS(O)₂N₃ 和 CHCl₂S(O)₂N₃ 的紫外激光光解（193nm 和 266nm）产生。两种氮烯均通过基质隔离 IR 和 EPR 光谱在固态 N₂（10K）和玻璃态甲苯（5K）基质中进行了表征。CH₂ClS(O)₂N（|/|=1.57cm 和 |/|=0.0026cm）和 CHCl₂S(O)₂N（|/|=1.56cm 和 |/|=0.0042cm）的三重基态多重性已得到证实。此外，还首次鉴定了由 CHCl₂S(O)₂N 中 SO₂ 消除形成的二氯甲基氮烯 CHCl₂N（|/|=1.57cm 和 |/|=0cm）。在紫外光照射（365nm）下，两种亚磺酰基氮烯 R⁻S(O)₂N（R=CH₂Cl 和 CHCl₂）分别经历同时的 1,2-R 迁移到 -磺酰胺 R⁻NSO₂ 和 1,2-氧迁移到 -亚硝基化合物 R⁻S(O)NO。这些新物种的鉴定通过 IR 光谱得到了 N 标记实验和 B3LYP/6-311++G（3df，3pd）水平的量子化学计算的支持。相比之下，热生成的亚磺酰基氮烯 CH₂ClS(O)₂N（600K）和 CHCl₂S(O)₂N（700K）在气相中完全解离，在这两种情况下，HCN、SO₂、HCl、HNSO 和 CO 形成。此外，在 CHCl₂S(O)₂N 的碎片产物中还鉴定出了 ClCN、OCCl₂、HNSO₂、•NSO₂和与大气相关的自由基•CHCl₂。基于实验观察到的产物和计算的势能曲线，讨论了 CH₂ClS(O)₂N 和 CHCl₂S(O)₂N 的重排和分解的潜在机制。
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