- Photochemistry of matrix isolated (Trifluoromethyl)sulfonyl azide, CF3SO2N3
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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.
- Zeng, Xiaoqing,Beckers, Helmut,Willner, Helge,Neuhaus, Patrik,Grote, Dirk,Sander, Wolfram
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p. 2281 - 2288
(2015/03/30)
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- Reaction of N-Chloro-N-fluoroperhaloalkylamines with Mercury. Facile Synthesis of N-Fluoro Imines and N-Fluoro Amines
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The reaction of N-chloro-N-fluoroalkylamines with mercury has been studied with ClCF2NClF, CF3NClF, CF3CF2NClF, CF3CF2CF2NClF, and (CF2NClF)2.In the absence of solvents, all but CF3NClF undergo dehalogenation to form the corresponding N-fluoro imines in good yield.Only the syn isomers of CF3CF=NF, CF3CF2CF=NF, and (CF=NF)2 are observed.With trifluoroacetic acid as a solvent, the reactions with mercury yield the corresponding N-fluoro amines ClCF2NHF, CF3NHF, CF3CF2NHF, and CF3CF2CF2NHF in excellent yields except with (CF2NClF)2.For the latter, the amine (CF2NHF)2eliminates HF under the reaction conditions, and only (CF=NF)2 is isolated.With trifluoroacetic anhydride as a solvent, ClCF2NClF is dehalogenated with mercury to give excellent yields of CF2=NF in the first practical synthesis of this simplest perfluoro imine.Details of these reactions and the characterization of the new compounds ClCF2NHF, CF3CF2NHF, CF3CF2CF2NHF, and CF3CF2CF=NF are presented.
- Sekiya, Akira,DesMarteau, Darryl D.
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p. 1277 - 1280
(2007/10/02)
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