Direct Observation of Carbamoylnitrenes

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• 作者：Hongmin Li ; Huabin Wan ; Zhuang Wu ; Dingqing Li ; Prof. Dr. Didier Bé ; gué ; Prof. Dr. Curt Wentrup and Prof. Dr. Xiaoqing Zeng
• 刊名：Chemistry - A European Journal
• 出版年：2016
• 出版时间：June 1, 2016
• 年：2016
• 卷：22
• 期：23
• 页码：7856-7862
• 全文大小：1231K
• ISSN：1521-3765

文摘

As the prototype Curtius rearrangement reaction, carbamoyl azide decomposes into aminoisocyanate and molecular nitrogen. However, the key intermediate carbamoylnitrene was previously undetected, even though the decomposition of carbamoyl azides has been studied frequently since its discovery in the 1890s. Upon ArF laser (λ=193 nm) photolysis, the stepwise decomposition of the two simplest carbamoyl azides H₂NC(O)N₃ and Me₂NC(O)N_3, isolated in solid noble gas matrices, occurs with the formation of the corresponding carbamoylnitrenes H₂NC(O)N and Me₂NC(O)N. Both triplet species are characterized for the first time by combining matrix-isolation IR spectroscopy and quantum-chemical calculations. Subsequent visible-light irradiations cause efficient rearrangement of these nitrenes into the respective aminoisocyanates.