Triplet Sensitized Photolysis of a Vinyl Azide: Direct Detection of a Triplet Vinyl Azide and Nitrene
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- 作者：Sridhar Rajam ; Abhijit V. Jadhav ; Qian Li ; Sujan K. Sarkar ; Pradeep N. D. Singh ; Ahleah Rohr ; Tamara C. S. Pace ; Rui Li ; Jeanette A. Krause ; Cornelia Bohne ; Bruce S. Ault ; Anna D. Gudmundsdottir
- 刊名：Journal of Organic Chemistry
- 出版年：2014
- 出版时间：October 3, 2014
- 年：2014
- 卷：79
- 期：19
- 页码：9325-9334
- 全文大小：666K
- ISSN：1520-6904
文摘
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 位max at 鈭?00 nm and a lifetime of 鈭? ms. Vinylnitrene 1c is formed with a rate constant of 4.25 脳 105 s鈥? from triplet 1,2-biradical 1b. Laser flash photolysis of 1 in oxygen-saturated acetonitrile results in 1c-O (位max = 430 nm, 蟿 鈮?420 渭s 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.