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Direct Observation of Carbamoylnitrenes
Author(s) -
Li Hongmin,
Wan Huabin,
Wu Zhuang,
Li Dingqing,
Bégué Didier,
Wentrup Curt,
Zeng Xiaoqing
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201600824
Subject(s) - nitrene , curtius rearrangement , azide , matrix isolation , photodissociation , decomposition , chemistry , photochemistry , matrix (chemical analysis) , nitrogen , spectroscopy , thermal decomposition , infrared spectroscopy , stereochemistry , organic chemistry , physics , catalysis , chromatography , quantum mechanics
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 H 2 NC(O)N 3 and Me 2 NC(O)N 3, isolated in solid noble gas matrices, occurs with the formation of the corresponding carbamoylnitrenes H 2 NC(O)N and Me 2 NC(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.