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, cilt.138, sa.47, ss.15287-15290, 2016 (SCI-Expanded) identifier identifier identifier

  • Yayın Türü: Makale / Tam Makale
  • Cilt numarası: 138 Sayı: 47
  • Basım Tarihi: 2016
  • Doi Numarası: 10.1021/jacs.6b07368
  • Dergi Adı: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
  • Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Sayfa Sayıları: ss.15287-15290
  • İstanbul Kültür Üniversitesi Adresli: Evet

Özet

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.