Gas-Phase Generation and Decomposition of a Sulfinylnitrene into the Iminyl Radical OSN

被引：33

作者：

Wu, Zhuang ^{[1
]}

Li, Dingqing ^{[1
]}

Li, Hongmin ^{[1
]}

Zhu, Bifeng ^{[1
]}

Sun, Hailong ^{[1
]}

Francisco, Joseph S. ^{[2
]}

Zeng, Xiaoqing ^{[1
]}

机构：

[1] Soochow Univ, Coll Chem Chem Engn & Mat Sci, Key Lab Hlth Chem & Mol Diag Suzhou, Suzhou 215123, Peoples R China

[2] Purdue Univ, Dept Chem, W Lafayette, IN 47907 USA

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2016年 / 55卷 / 04期

基金：

中国国家自然科学基金;

关键词：

azides; density functional calculations; IR spectroscopy; matrix isolation; nitrenes; INFRARED-SPECTRA; BENZENESULFINYL AZIDE; MATRIX-ISOLATION; SOLID ARGON; ISOMERS; PHOTOLYSIS; SULFUR; PHOTOCHEMISTRY; IDENTIFICATION; REARRANGEMENT;

D O I：

10.1002/anie.201510105

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The dipolar oxathiazyne-like sulfinylnitrene RS(O) N, a highly reactive alpha-oxo nitrene, has been rarely investigated. Upon flash vacuum pyrolysis of sulfinyl azide CF3S(O) N-3 at 350 degrees 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 degrees 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) N-3.

引用

页码：1507 / 1510

页数：4

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