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Trifluoromethyl azide decomposes in a low-pressure flow system at rather high temperatures by splitting off N2. The nature of the resulting products depends largely on the wall material of the pyrolysis tube: using molybdenum above 1120 K, FCN is observed exclusively. Neither F2C=NF nor F3C-N=N-CF3 can be detected as intermediates by comparing their PE spectra with those continuously recorded while increasing the temperature. F3C-N = N - CF3 fragments already at 870 K to give N2 and F3C-CF3. The PE spectra of F3CN3 and F2C=NF are assigned based on MNDO calculations.
The neutral title compound, 8,8-bis(dimethylamino)dibenzo-[a,d]-heptafulvene, exhibits a first vertical ionization potential of only 6.98 eV and, therefore, can also be oxidized by AlCl3 in H2CCl2 solution. The radical cation generated shows a complex multiplet signal pattern, which is assigned based on additional ENDOR measurements. The photoelectron (PE) and ESR spectra of the 112 valence electron molecule are interpreted by “pararneter-optimized” HMO and by geometry-optimized MNDO calculations, which both suggest a non-planar π-type ground state with most of the charge and the spin distributed over the dibenzoheptatriene part of the radical cation.
Photoelectron (PE) spectra of ethylene and vinylene carbonates and thiocarbonates as well as of methylene trithiocarbonate and some open-chain derivatives are reported.
The low energy bands, well separated in the unsaturated compounds, are assigned to lone pair and π type ionizations. The assignment is based on comparison of PE spectra, modified CNDO calculations, and sulfur Κβ emission spectra. The pronounced substituent effects due to which the first ionization potential varies from 8.4 eV to 11.1 eV are discussed.