title: Triplet sensitized photolysis of a vinyl azide: direct detection of a triplet vinyl azide and nitrene.
abstract: Photolysis of vinylazide 1, which has a built-in acetophenone triplet sensitizer, in argon-saturated toluene results in azirine 2, whereas irradiation in oxygen-saturated toluene yields cyanide derivatives 3 and 4. Laser flash photolysis of azide 1 in argon-saturated acetonitrile shows formation of vinylnitrene 1c, which has a λmax at ∼300 nm and a lifetime of ∼1 ms. Vinylnitrene 1c is formed with a rate constant of 4.25 × 10(5) s(-1) from triplet 1,2-biradical 1b. Laser flash photolysis of 1 in oxygen-saturated acetonitrile results in 1c-O (λmax = 430 nm, τ ≈ 420 μs acetonitrile). Density functional theory (DFT) calculations were used to aid in the characterization of the intermediates formed upon irradiation of azide 1 and to validate the proposed mechanism for its photoreactivity.
authors.affiliation: Department of Chemistry, University of Cincinnati , Cincinnati, Ohio 45221-0172, United States.
authors.forename: Sridhar
authors.initials: S
authors.lastname: Rajam
authors.forename: Abhijit V
authors.initials: AV
authors.lastname: Jadhav
authors.forename: Qian
authors.initials: Q
authors.lastname: Li
authors.forename: Sujan K
authors.initials: SK
authors.lastname: Sarkar
authors.forename: Pradeep N D
authors.initials: PN
authors.lastname: Singh
authors.forename: Ahleah
authors.initials: A
authors.lastname: Rohr
authors.forename: Tamara C S
authors.initials: TC
authors.lastname: Pace
authors.forename: Rui
authors.initials: R
authors.lastname: Li
authors.forename: Jeanette A
authors.initials: JA
authors.lastname: Krause
authors.forename: Cornelia
authors.initials: C
authors.lastname: Bohne
authors.forename: Bruce S
authors.initials: BS
authors.lastname: Ault
authors.forename: Anna D
authors.initials: AD
authors.lastname: Gudmundsdottir