title: Triplet-sensitized photoreactivity of a geminal diazidoalkane.
abstract: Photolysis of 1 in chloroform yielded 2 as the major product and a small quantity of 3. Laser flash photolysis demonstrated that upon irradiation, the first excited triplet state of the ketone (T(1K)) of 1 is formed and decayed to form radical 4, which has a λ(max) at 380 nm (τ = 2 μs). Radical 4 expelled a nitrogen molecule to yield imine radical 5 (λ(max) at 300 nm). Density functional theory (DFT) calculations showed that the transition state barrier for the formation of 5 is approximately 4 kcal/mol. In comparison, photolysis of 1 in argon matrices resulted in triplet nitrene 6, which was further characterized with (15)N and D isotope labeling and DFT calculations. Prolonged irradiation of 6 yields triplet imine nitrene 7.
authors: Department of Chemistry, University of Cincinnati, Cincinnati, Ohio 45221-0172, United States.
authors: Ranaweera A A Upul
authors: RA
authors: Ranaweera
authors: Jagadis
authors: J
authors: Sankaranarayanan
authors: Lydia
authors: L
authors: Casey
authors: Bruce S
authors: BS
authors: Ault
authors: Anna D
authors: AD
authors: Gudmundsdottir