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Published on: September 8, 2013
Gas-Phase Generation and Decomposition of a Sulfinylnitrene into the Iminyl Radical OSN
Zhuang Wu1, Dingqing Li1, Hongmin Li1
1The Key Lab of Health Chemistry and Molecular Diagnosis of Suzhou, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, 215123, China.
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.
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