Molecules, Vol. 23, Pages 3312: Chloro- and Dichloro-methylsulfonyl Nitrenes: Spectroscopic Characterization, Photoisomerization, and Thermal Decomposition

Molecules, Vol. 23, Pages 3312: Chloro- and Dichloro-methylsulfonyl Nitrenes: Spectroscopic Characterization, Photoisomerization, and Thermal Decomposition
Molecules doi: 10.3390/molecules23123312
Authors:
Yang Yang
Xianxu Chu
Yan Lu
Manabu Abe
Xiaoqing Zeng

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...

Source: Molecules - December 13, 2018 Category: Chemistry Authors: Yang Yang Xianxu Chu Yan Lu Manabu Abe Xiaoqing Zeng Tags: Article Source Type: research