title: Gas-Phase Generation and Decomposition of a Sulfinylnitrene into the Iminyl Radical OSN.
abstract: The dipolar oxathiazyne-like sulfinylnitrene RS(O)N, a highly reactive α-oxo nitrene, has been rarely investigated. Upon flash vacuum pyrolysis of sulfinyl azide CF3S(O)N3 at 350 °C, an elusive sulfinylnitrene CF3S(O)N was generated in the gas phase in its singlet ground state and was characterized by matrix-isolation IR spectroscopy. Further fragmentation of CF3S(O)N at 600 °C produced CF3 and a novel iminyl radical OSN, an SO2 analogue, which were unambiguously identified by IR spectroscopy. Consistent with the experimental observations, DFT calculations clearly support a stepwise decomposition mechanism of CF3S(O)N3.
authors.affiliation: The Key Lab of Health Chemistry and Molecular Diagnosis of Suzhou, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, 215123, China.
authors.forename: Zhuang
authors.initials: Z
authors.lastname: Wu
authors.affiliation: The Key Lab of Health Chemistry and Molecular Diagnosis of Suzhou, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, 215123, China.
authors.forename: Dingqing
authors.initials: D
authors.lastname: Li
authors.affiliation: The Key Lab of Health Chemistry and Molecular Diagnosis of Suzhou, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, 215123, China.
authors.forename: Hongmin
authors.initials: H
authors.lastname: Li
authors.affiliation: The Key Lab of Health Chemistry and Molecular Diagnosis of Suzhou, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, 215123, China.
authors.forename: Bifeng
authors.initials: B
authors.lastname: Zhu
authors.affiliation: The Key Lab of Health Chemistry and Molecular Diagnosis of Suzhou, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, 215123, China.
authors.forename: Hailong
authors.initials: H
authors.lastname: Sun
authors.affiliation: Department of Chemistry, Purdue University, West Lafayette, IN, 47907, USA.
authors.forename: Joseph S
authors.initials: JS
authors.lastname: Francisco
authors.affiliation: The Key Lab of Health Chemistry and Molecular Diagnosis of Suzhou, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, 215123, China. xqzeng@suda.edu.cn.
authors.forename: Xiaoqing
authors.initials: X
authors.lastname: Zeng
keywords: IR spectroscopy; azides; density functional calculations; matrix isolation; nitrenes