3,4,5,6-Tetrafluorophenylnitren-2-yl: a ground-state quartet triradical.
The photochemistry of 2-iodo-3,4,5,6-tetrafluorophenyl azide (7 d) has been investigated in argon and neon matrices at 4 K, and the products characterized by IR and EPR spectroscopy. The primary photochemical step is loss of a nitrogen molecule and formation of phenyl nitrene 1 d. Further irradiation with UV or visible light results in mixtures of 1 d with azirine 5 d', ketenimine 6 d', nitreno radical 2 d, and azirinyl radical 9. The relative amounts of these products strongly depend on the matrix and on the irradiation conditions. Nitreno radical 2 d with a quartet ground state was characterized by EPR spectroscopy. Electronic structure calculations in combination with the experimental results allow for a detailed understanding of the properties of this unusual new type of organic high-spin molecules.
Lehrstuhl für Organische Chemie II, Ruhr-Universität Bochum, 44780 Bochum (Germany), Fax: (+49) 234-321-4353.
Dirk
D
Grote
Christopher
C
Finke
Simone
S
Kossmann
Frank
F
Neese
Wolfram
W
Sander
EPR spectroscopy; IR spectroscopy; matrix isolation; photochemistry; radicals