High-spin intermediates of the photolysis of 2,4,6-triazido-3-chloro-5-fluoropyridine.

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 = -0.003

SUBMITTER: Chapyshev SV 

PROVIDER: S-EPMC3678571 | biostudies-literature | 2013

REPOSITORIES: biostudies-literature