Solution phase isomerization of vibrationally excited singlet nitrenes to vibrationally excited 1,2-didehydroazepine.
Photolysis of phenyl and o-biphenylyl azide (at 270 nm) releases vibrationally excited singlet nitrene which isomerizes to the corresponding hot 1,2-didehydroazepine at a rate competitive with thermal relaxation. Using ultrafast vibrational spectroscopy we observe the formation of vibrationally excited 1,2-4,6-azacycloheptatetraene (1,2-didehydroazepine) in picoseconds following photolysis of phenyl azide in chloroform and o-biphenylyl azide in acetonitrile at ambient temperature.
Burdzinski
Gotard T
GT
Department of Chemistry, Ohio State University Center for Chemical and Biophysical Dynamics, 100 West 18th Avenue, Columbus, OH 43210, USA.
Middleton
Chris T
CT
Gustafson
Terry L
TL
Platz
Matthew S
MS