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

Nunes C. M., Knezz S. N., Reva I., Fausto R., McMahon R. J.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol.138, no.47, pp.15287-15290, 2016 (SCI-Expanded) identifier identifier identifier

  • Publication Type: Article / Article
  • Volume: 138 Issue: 47
  • Publication Date: 2016
  • Doi Number: 10.1021/jacs.6b07368
  • Journal Name: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Page Numbers: pp.15287-15290
  • Istanbul Kültür University Affiliated: Yes

Abstract

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.