Evidence of a Nitrene Tunneling Reaction: Spontaneous Rearrangement of 2-Formyl Phenylnitrene to an Imino Ketene in Low-Temperature Matrixes.
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.
CQC, Department of Chemistry, University of Coimbra , 3004-535 Coimbra, Portugal.
Cláudio M
CM
Nunes
Department of Chemistry, University of Wisconsin-Madison , 1101 University Avenue, Madison, Wisconsin 53706-1322, United States.
Stephanie N
SN
Knezz
CQC, Department of Chemistry, University of Coimbra , 3004-535 Coimbra, Portugal.
Igor
I
Reva
CQC, Department of Chemistry, University of Coimbra , 3004-535 Coimbra, Portugal.
Rui
R
Fausto
Department of Chemistry, University of Wisconsin-Madison , 1101 University Avenue, Madison, Wisconsin 53706-1322, United States.
Robert J
RJ
McMahon