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• W2104861889 endingPage "742" @default.
• W2104861889 startingPage "733" @default.
• W2104861889 abstract "In contrast to theoretical expectations, the photolysis of 2,4,6-triazido-3-chloro-5-fluoropyridine in argon at 5 K gives rise to EPR peaks of just two triplet mononitrenes, two quintet dinitrenes, and a septet trinitrene. EPR spectral simulations in combination with DFT calculations show that observable nitrenes can be assigned to triplet 2,4-diazido-3-chloro-5-fluoropyridyl-6-nitrene ( D T = 1.026 cm −1 , E T = 0), triplet 2,6-diazido-3-chloro-5-fluoropyridyl-4-nitrene ( D T = 1.122 cm −1 , E T = 0.0018 cm −1 ), quintet 4-azido-3-chloro-5-fluoropyridyl-2,6-dinitrene ( D Q = 0.215 cm −1 , E Q = 0.0545 cm −1 ), quintet 2-azido-3-chloro-5-fluoropyridyl-4,6-dinitrene ( D Q = 0.209 cm −1 , E Q = 0.039 cm −1 ) and septet 3-chloro-5-fluoropyridyl-2,4,6-trinitrene ( D S = −0.1021 cm −1 , E S = −0.0034 cm −1 ). Preferential photodissociation of the azido groups located in ortho -positions to the fluorine atom of pyridines is associated with strong π-conjugation of these groups with the pyridine ring. On photoexcitation, such azido groups are more efficiently involved in reorganization of the molecular electronic system and more easily adopt geometries of the locally excited predissociation states." @default.
• W2104861889 created "2016-06-24" @default.
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• W2104861889 date "2013-04-16" @default.
• W2104861889 modified "2023-10-16" @default.
• W2104861889 title "High-spin intermediates of the photolysis of 2,4,6-triazido-3-chloro-5-fluoropyridine" @default.
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• W2104861889 doi "https://doi.org/10.3762/bjoc.9.83" @default.
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