title: The decomposition of benzenesulfonyl azide: a matrix isolation and computational study.
abstract: The thermal-decomposition and photo-decomposition of benzenesulfonyl azide, PhS(O)2N3, have been studied by combining matrix-isolation IR spectroscopy and quantum chemical calculations. Upon flash vacuum pyrolysis at 800 K, the azide splits off molecular nitrogen and exclusively furnishes phenylnitrene (PhN) and SO2in the gas phase. In contrast, the azide favors stepwise photodecomposition in solid Ar and Ne matrices at 2.8 K. Specifically, the UV laser photolysis (193 and 266 nm) of PhS(O)2N3results in the formation of the key nitrene intermediate PhS(O)2N in the triplet ground state, which undergoes pseudo-Curtius rearrangement into N-sulfonyl imine PhNSO2under subsequent visible light irradiation (380-450 nm). Further fragmentation of PhNSO2into SO2and PhN followed by ring-expansion to didehydroazepine also occurs upon visible light irradiation. The preference of the stepwise mechanism for the decomposition of PhS(O)2N3is supported by quantum chemical calculations using DFT B3LYP/6-311++G(3df,3pd) and CBS-QB3 methods.
authors.affiliation: College of Chemistry, Chemical Engineering and Materials Science, Soochow University, 215123 Suzhou, P. R. China. xqzeng@suda.edu.cn.
authors.forename: Guohai
authors.initials: G
authors.lastname: Deng
authors.affiliation: College of Chemistry, Chemical Engineering and Materials Science, Soochow University, 215123 Suzhou, P. R. China. xqzeng@suda.edu.cn.
authors.forename: Xuelin
authors.initials: X
authors.lastname: Dong
authors.affiliation: College of Chemistry, Chemical Engineering and Materials Science, Soochow University, 215123 Suzhou, P. R. China. xqzeng@suda.edu.cn.
authors.forename: Qifan
authors.initials: Q
authors.lastname: Liu
authors.affiliation: College of Chemistry, Chemical Engineering and Materials Science, Soochow University, 215123 Suzhou, P. R. China. xqzeng@suda.edu.cn.
authors.forename: Dingqing
authors.initials: D
authors.lastname: Li
authors.affiliation: College of Chemistry, Chemical Engineering and Materials Science, Soochow University, 215123 Suzhou, P. R. China. xqzeng@suda.edu.cn.
authors.forename: Hongmin
authors.initials: H
authors.lastname: Li
authors.affiliation: School for Radiological and Interdisciplinary Sciences, Soochow University, 215123 Suzhou, P. R. China.
authors.forename: Qiao
authors.initials: Q
authors.lastname: Sun
authors.affiliation: College of Chemistry, Chemical Engineering and Materials Science, Soochow University, 215123 Suzhou, P. R. China. xqzeng@suda.edu.cn.
authors.forename: Xiaoqing
authors.identifier: http://orcid.org/0000-0003-4611-2094
authors.initials: X
authors.lastname: Zeng