title: Vinylnitrene formation from 3,5-diphenyl-isoxazole and 3-benzoyl-2-phenylazirine.
abstract: Photolysis of 1 in argon-saturated acetonitrile yields 2, whereas in oxygen-saturated acetonitrile small amounts of benzoic acid and benzamide are formed in addition to 2. Similarly, photolysis of 2 in argon-saturated acetonitrile results in 1 and a trace amount of 3, whereas in oxygen-saturated acetonitrile the major product is 1 in addition to the formation of small amounts of benzoic acid and benzamide. Laser flash photolysis of 1 results in an absorption due to triplet vinylnitrene 4 (broad absorption with λ(max) at 360 nm, τ = 1.8 μs, acetonitrile) that is formed with a rate constant of 1.2 × 10(7) s(-1) and decays with a rate constant of 5.6 × 10(5) s(-1). Laser flash photolysis of 2 in argon-saturated acetonitrile likewise results in the formation of triplet vinylnitrene 4 but also ylide 5 (λ(max) at 440 nm, τ = 13 μs). The rate constant for forming 4 in argon-saturated acetonitrile is 1.6 × 10(7) s(-1). In oxygen-saturated acetonitrile, vinylnitrene 4 reacts to form the peroxide radical 6 (λ(max) 360 nm, ~0.7 μs, acetonitrile) at a rate of 2 × 10(9) M(-1) s(-1). Density functional theory calculations were performed to aid in the characterization of vinylnitrene 4 and peroxide 6 and to support the proposed mechanism for the formation of these intermediates.
authors.affiliation: Department of Chemistry, University of Cincinnati , Cincinnati Ohio 45221-0172, United States.
authors.forename: Disnani W
authors.initials: DW
authors.lastname: Gamage
authors.forename: Qian
authors.initials: Q
authors.lastname: Li
authors.forename: R A A Upul
authors.initials: RA
authors.lastname: Ranaweera
authors.forename: Sujan K
authors.initials: SK
authors.lastname: Sarkar
authors.forename: Geethika K
authors.initials: GK
authors.lastname: Weragoda
authors.forename: Patrick L
authors.initials: PL
authors.lastname: Carr
authors.forename: Anna D
authors.initials: AD
authors.lastname: Gudmundsdottir