Evidence of a Nitrene Tunneling Reaction: Spontaneous Rearrangement of 2-Formyl Phenylnitrene to an Imino Ketene in Low-Temperature Matrixes

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• 作者：Cláudio M. Nunes ; Stephanie N. Knezz ; Igor Reva ; Rui Fausto ; Robert J. McMahon
• 刊名：Journal of the American Chemical Society
• 出版年：2016
• 出版时间：November 30, 2016
• 年：2016
• 卷：138
• 期：47
• 页码：15287-15290
• 全文大小：298K
• ISSN：1520-5126

文摘

Triplet 2-formyl phenylnitrene was generated by photolysis of 2-formyl phenylazide isolated in Ar, Kr, and Xe matrixes and characterized by IR, UV–vis, and EPR spectroscopies. Upon generation at 10 K, the triplet nitrene spontaneously rearranges in the dark to singlet 6-imino-2,4-cyclohexadien-1-ketene on the time scale of several hours. The intramolecular [1,4] H atom shift from the nitrene to the imino ketene occurs by tunneling, on the triplet manifold, followed by intersystem crossing. This case constitutes the first direct evidence of a tunneling reaction involving a nitrene.