Direct Observation of Carbamoylnitrenes.
Identifieur interne : 002091 ( Main/Merge ); précédent : 002090; suivant : 002092Direct Observation of Carbamoylnitrenes.
Auteurs : Hongmin Li [République populaire de Chine] ; Huabin Wan [République populaire de Chine] ; Zhuang Wu [République populaire de Chine] ; Dingqing Li [République populaire de Chine] ; Didier Bégué [France] ; Curt Wentrup [Australie] ; Xiaoqing Zeng [République populaire de Chine]Source :
- Chemistry (Weinheim an der Bergstrasse, Germany) [ 1521-3765 ] ; 2016.
Abstract
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 H2 NC(O)N3 and Me2 NC(O)N3, isolated in solid noble gas matrices, occurs with the formation of the corresponding carbamoylnitrenes H2 NC(O)N and Me2 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.
DOI: 10.1002/chem.201600824
PubMed: 27105905
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China.</nlm:affiliation><country xml:lang="fr" wicri:curation="lc">République populaire de Chine</country><wicri:regionArea>The Key Lab of Health Chemistry and Molecular Diagnosis of Suzhou, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, 215123</wicri:regionArea><wicri:noRegion>215123</wicri:noRegion></affiliation></author><author><name sortKey="Wan, Huabin" sort="Wan, Huabin" uniqKey="Wan H" first="Huabin" last="Wan">Huabin Wan</name><affiliation wicri:level="1"><nlm:affiliation>The Key Lab of Health Chemistry and Molecular Diagnosis of Suzhou, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, 215123, P.R. China.</nlm:affiliation><country xml:lang="fr" wicri:curation="lc">République populaire de Chine</country><wicri:regionArea>The Key Lab of Health Chemistry and Molecular Diagnosis of Suzhou, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, 215123</wicri:regionArea><wicri:noRegion>215123</wicri:noRegion></affiliation></author><author><name sortKey="Wu, Zhuang" sort="Wu, Zhuang" uniqKey="Wu Z" first="Zhuang" last="Wu">Zhuang Wu</name><affiliation wicri:level="1"><nlm:affiliation>The Key Lab of Health Chemistry and Molecular Diagnosis of Suzhou, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, 215123, P.R. China.</nlm:affiliation><country xml:lang="fr" wicri:curation="lc">République populaire de Chine</country><wicri:regionArea>The Key Lab of Health Chemistry and Molecular Diagnosis of Suzhou, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, 215123</wicri:regionArea><wicri:noRegion>215123</wicri:noRegion></affiliation></author><author><name sortKey="Li, Dingqing" sort="Li, Dingqing" uniqKey="Li D" first="Dingqing" last="Li">Dingqing Li</name><affiliation wicri:level="1"><nlm:affiliation>The Key Lab of Health Chemistry and Molecular Diagnosis of Suzhou, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, 215123, P.R. China.</nlm:affiliation><country xml:lang="fr" wicri:curation="lc">République populaire de Chine</country><wicri:regionArea>The Key Lab of Health Chemistry and Molecular Diagnosis of Suzhou, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, 215123</wicri:regionArea><wicri:noRegion>215123</wicri:noRegion></affiliation></author><author><name sortKey="Begue, Didier" sort="Begue, Didier" uniqKey="Begue D" first="Didier" last="Bégué">Didier Bégué</name><affiliation wicri:level="1"><nlm:affiliation>Institut des Sciences Analytiques et de Physico-Chimie pour l'Environnement et les Matériaux (IPREM), Université de Pau et des Pays de l'Adour, 64000, Pau, France.</nlm:affiliation><country xml:lang="fr">France</country><wicri:regionArea>Institut des Sciences Analytiques et de Physico-Chimie pour l'Environnement et les Matériaux (IPREM), Université de Pau et des Pays de l'Adour, 64000, Pau</wicri:regionArea><wicri:noRegion>64000, Pau</wicri:noRegion><wicri:noRegion>64000, Pau</wicri:noRegion></affiliation></author><author><name sortKey="Wentrup, Curt" sort="Wentrup, Curt" uniqKey="Wentrup C" first="Curt" last="Wentrup">Curt Wentrup</name><affiliation wicri:level="1"><nlm:affiliation>School of Chemistry and Molecular Biosciences, The University of Queensland, 4072, Brisbane, Queensland, Australia. wentrup@uq.edu.au.</nlm:affiliation><country xml:lang="fr">Australie</country><wicri:regionArea>School of Chemistry and Molecular Biosciences, The University of Queensland, 4072, Brisbane, Queensland</wicri:regionArea><wicri:noRegion>Queensland</wicri:noRegion></affiliation></author><author><name sortKey="Zeng, Xiaoqing" sort="Zeng, Xiaoqing" uniqKey="Zeng X" first="Xiaoqing" last="Zeng">Xiaoqing Zeng</name><affiliation wicri:level="1"><nlm:affiliation>The Key Lab of Health Chemistry and Molecular Diagnosis of Suzhou, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, 215123, P.R. China. xqzeng@suda.edu.cn.</nlm:affiliation><country wicri:rule="url">République populaire de Chine</country></affiliation></author></analytic><series><title level="j">Chemistry (Weinheim an der Bergstrasse, Germany)</title><idno type="eISSN">1521-3765</idno><imprint><date when="2016" type="published">2016</date></imprint></series></biblStruct></sourceDesc></fileDesc><profileDesc><textClass></textClass></profileDesc></teiHeader><front><div type="abstract" xml:lang="en">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 H2 NC(O)N3 and Me2 NC(O)N3, isolated in solid noble gas matrices, occurs with the formation of the corresponding carbamoylnitrenes H2 NC(O)N and Me2 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.</div></front></TEI></record>Pour manipuler ce document sous Unix (Dilib)
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