J. Am. Chem. Soc. 2001, 123, 7923-7924
Synthesis and Characterization of a Distonic Nitrene Ion: Gas-Phase Reactivity of Singlet and Triplet N-Phenyl-3-Nitrenopyridinium Ion
7923
Scheme 1
Shane E. Tichy,* Brian T. Hill,† J. Larry Campbell, and Hilkka I. Kentta¨maa The Department of Chemistry, Purdue UniVersity West Lafayette, Indiana 47907-1393
Scheme 2
ReceiVed February 22, 2001 ReVised Manuscript ReceiVed June 27, 2001 The intermediates produced upon photolysis and thermolysis of phenyl azide have been studied extensively by a variety of experimental techniques.1 Photolysis of phenyl azide in solution produces open-shell singlet phenylnitrene whose lifetime (∼1 ns) depends on the temperature at which it is generated. At ambient temperature, singlet phenylnitrene rapidly ring-expands to azacycloheptatetraene via the intermediacy of azabicyclo[4.1.0]heptatriene. The ring-expanded species is responsible for the observed bimolecular reactivity.2 However, at lower temperatures (
