TY - JOUR
T1 - Evidence of a Nitrene Tunneling Reaction
T2 - Spontaneous Rearrangement of 2-Formyl Phenylnitrene to an Imino Ketene in Low-Temperature Matrixes
AU - Nunes, Cláudio M.
AU - Knezz, Stephanie N.
AU - Reva, Igor
AU - Fausto, Rui
AU - McMahon, Robert J.
N1 - Funding Information:
This work was supported by the Portuguese Fundacao para a Ciencia e a Tecnologia (FCT). The Coimbra Chemistry Centre is supported by the FCT through the project UID/QUI/0313/2013, cofunded by COMPETE. C.M.N. and I.R. acknowledge the FCT for Postdoctoral Grant No. SFRH/BPD/86021/2012 and Investigador FCT Grant, respectively. R.J.M. gratefully acknowledges the U.S. National Science Foundation for support of this project (CHE-1362264) and the EPR spectrometer (CHE-0741901).
Publisher Copyright:
© 2016 American Chemical Society.
PY - 2016/11/30
Y1 - 2016/11/30
N2 - 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.
AB - 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.
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U2 - 10.1021/jacs.6b07368
DO - 10.1021/jacs.6b07368
M3 - Article
C2 - 27682681
AN - SCOPUS:85000398933
SN - 0002-7863
VL - 138
SP - 15287
EP - 15290
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 47
ER -