Photochemistry of Matrix Isolated (Trifluoromethyl)sulfonyl Azide, CF3SO2N3

The photochemistry of matrix isolated (trifluoromethylsulfonyl) azide, CF3SO2N3, has been studied at low temperatures. Upon ArF laser irradiation (λ = 193 nm), the azide eliminates N2 and furnishes triplet [(trifluoromethyl)sulfonyl]nitrene, CF3SO2N, which has been characterized by IR and EPR spectr...

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Bibliographic Details
Published in:	The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 119; no. 11; pp. 2281 - 2288
Main Authors:	Zeng, Xiaoqing, Beckers, Helmut, Willner, Helge, Neuhaus, Patrik, Grote, Dirk, Sander, Wolfram
Format:	Journal Article
Language:	English
Published:	American Chemical Society 19-03-2015
Online Access:	Get full text
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Summary:	The photochemistry of matrix isolated (trifluoromethylsulfonyl) azide, CF3SO2N3, has been studied at low temperatures. Upon ArF laser irradiation (λ = 193 nm), the azide eliminates N2 and furnishes triplet [(trifluoromethyl)sulfonyl]nitrene, CF3SO2N, which has been characterized by IR and EPR spectroscopy. Upon subsequent UV light irradiation (λ = 260–400 nm) the nitrene converts to CF3NSO2 and CF3S(O)NO through a Curtius-type rearrangement. Further two new species CF2NSO2F and FSNO were identified together with CF2NF, SO2, F2CO, CF3NO, and SO as side products. In addition, triplet nitrene CF3N was detected by its EPR and IR spectra. The complex stepwise photodecomposition of matrix isolated CF3SO2N3 is discussed in terms of the observed photolysis products and quantum chemical calculations.
ISSN:	1089-5639 1520-5215
DOI:	10.1021/jp506243s