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Gas‐Phase Generation and Decomposition of a Sulfinylnitrene into the Iminyl Radical OSN
Author(s) -
Wu Zhuang,
Li Dingqing,
Li Hongmin,
Zhu Bifeng,
Sun Hailong,
Francisco Joseph S.,
Zeng Xiaoqing
Publication year - 2016
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201510105
Subject(s) - nitrene , matrix isolation , flash vacuum pyrolysis , azide , chemistry , spectroscopy , decomposition , infrared spectroscopy , singlet state , fragmentation (computing) , radical , gas phase , photochemistry , pyrolysis , organic chemistry , physics , atomic physics , operating system , quantum mechanics , computer science , excited state , catalysis
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 CF 3 S(O)N 3 at 350 °C, an elusive sulfinylnitrene CF 3 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 CF 3 S(O)N at 600 °C produced CF 3 and a novel iminyl radical OSN, an SO 2 analogue, which were unambiguously identified by IR spectroscopy. Consistent with the experimental observations, DFT calculations clearly support a stepwise decomposition mechanism of CF 3 S(O)N 3 .