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Open AccessArticle

Chloro- and Dichloro-methylsulfonyl Nitrenes: Spectroscopic Characterization, Photoisomerization, and Thermal Decomposition

1
College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China
2
Department of Chemistry, Graduate School of Science, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8526, Japan
*
Authors to whom correspondence should be addressed.
Academic Editor: Xuefeng Wang
Molecules 2018, 23(12), 3312; https://doi.org/10.3390/molecules23123312
Received: 27 November 2018 / Revised: 11 December 2018 / Accepted: 12 December 2018 / Published: 13 December 2018
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 (|D/hc| = 1.57 cm−1 and |E/hc| = 0.0026 cm−1) and CHCl2S(O)2N (|D/hc| = 1.56 cm−1 and |E/hc| = 0.0042 cm−1) has been confirmed. In addition, dichloromethylnitrene CHCl2N (|D/hc| = 1.57 cm−1 and |E/hc| = 0 cm−1), 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 N-sulfonlyamines R–NSO2 and 1,2-oxygen shift to S-nitroso compounds R–S(O)NO, respectively. The identification of these new species with IR spectroscopy is supported by 15N 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. View Full-Text
Keywords: azides; nitrenes; decomposition; matrix isolation; photoisomerization; reaction mechanism azides; nitrenes; decomposition; matrix isolation; photoisomerization; reaction mechanism
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MDPI and ACS Style

Yang, Y.; Chu, X.; Lu, Y.; Abe, M.; Zeng, X. Chloro- and Dichloro-methylsulfonyl Nitrenes: Spectroscopic Characterization, Photoisomerization, and Thermal Decomposition. Molecules 2018, 23, 3312.

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