Gas‐Phase Generation and Decomposition of a Sulfinylnitrene into the Iminyl Radical OSN. (17th December 2015)

• Record Type: Journal Article
• Authors: Wu, Zhuang; Li, Dingqing; Li, Hongmin; Zhu, Bifeng; Sun, Hailong; Francisco, Joseph S.; Zeng, Xiaoqing
• Is Part Of: Angewandte Chemie. Volume 128:Number 4(2016)
• Page Start: 1529
• Page End: 1532
• Publication Date: 2015-12-17
• Subjects: Azide -- Dichtefunktionalrechnungen -- IR-Spektroskopie -- Matrixisolierung -- Nitrene; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201510105
• Languages: English
• ISSNs: 0044-8249

Abstract

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 CF3 S(O)N3 at 350 °C, an elusive sulfinylnitrene CF3 S(O)N was generated in the gas phase in its singlet ground state and was characterized by matrix‐isolation IR spectroscopy. Further fragmentation of CF3 S(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 CF3 S(O)N3 .