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G. Argüello, H. Grothe, M. Kronberg, H. Willner, H. Mack:
"IR and Visible Absorption Spectrum of the Fluoroformyloxyl Radical, FCO2, Isolated in Inert Gas Matrices";
Journal of Physical Chemistry, 99 (1995), S. 17525 - 17533.

Vacuum flash pyrolysis of bis(fluoroformyl) peroxide, FC(O)OOC(O)F, diluted in N₂, Ar, or Ne, yields on subsequent quenching of the products in a matrix at 10, 14, or 6 K, respectively, the fluoroformyloxyl radical, FCO₂, in the X²B₂ ground state. It has been possible to record its infrared spectrum and to identify all bands by their photochemical behavior for the first time. The assignment of the six fundamental vibrations on the basis of C_2v symmetry (a₁ 1475, 960, 519; b_l 1098,474, b₂ 735 cm^-1; Ne matrix) was achieved by a normal coordinate analysis taking into account additional data of ¹⁸O- or ¹³C-labeled FCO₂. The experimental fundamental vibrations and the structural parameters derived from the vibrational data are compared to the results of ab initio and DFT (density functional theory) calculations. The visible spectrum of FCO₂ isolated in a neon matrix agrees with the known gas phase spectrum. The origin of the B²A₁ - X²B₂ transition is observed at 13103 cm^-1, and four fundamentals at 1607, 1117, 839, and 611 cm^-1 are detected due to the excited state species (B²A₁). In a fast reaction with NO, the FCO₂ radical quantitatively forms FNO and C0₂. The anticipated intermediate FC(0)ONO is not observed.

http://dx.doi.org/10.1021/j100049a010

http://pubs.acs.org/doi/pdf/10.1021/j100049a010