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Thermally Persistent Carbonyl Nitrene: FC(O)N

Hailong Sun^†,   Bifeng Zhu^†,   Zhuang Wu^†,   Xiaoqing Zeng^*†(曾小庆),   Helmut Beckers^‡  and   William S. Jenks^*§  

^† College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Jiangsu 215123, China

^‡ Institut für Chemie und Biochemie, Freie Universität Berlin, D-14195 Berlin, Germany

^§ Department of Chemistry, Iowa State University, Ames, Iowa 50011-3111, United States

J. Org. Chem. 2015, 80, 2006–2009

Transient carbonyl nitrenes RC(O)N, formed during thermal- or photoinduced decomposition of carbonyl azides RC(O)N₃, are highly liable to the Curtius rearrangement, producing isocyanates RNCO in almost quantitative yield. Contrary to common belief, we found a thermally persistent triplet carbonyl nitrene, FC(O)N, that can be produced by flash pyrolysis of FC(O)N₃ in 49% yield. The computed CBS-QB3 activation barrier for the thermal decomposition of FC(O)N₃ to FC(O)N is 29 kJ mol–1 lower than that for a concerted pathway producing FNCO.

链接：

//pubs.acs.org/doi/abs/10.1021/jo502821y