INTERCONVERSION STUDIES AND CHARACTERIZATION OF ASYMMETRIC AND SYMMETRIC DINITROGEN TRIOXIDE IN NITRIC-OXIDE MATRICES BY RAMAN AND INFRARED-SPECTROSCOPY
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The first laser Raman spectra of both asymmetric dinitrogen trioxide (O2NNO) and symmetric dinitrogen trioxide (ONONO) have been collected by stabilizing these species in nitric oxide matrices at 12 K. Laser irradiation at wavelengths from 5682 to 7526 converts as-N2O3 to s-N2O3 but wavelengths of 5145 or 4880 convert the symmetric isomer back to the asymmetric one. The Raman data along with the infrared spectra of several isotopic species (with 15N and/or 18O) for both molecules made it possible to resolve previous ambiguities in the vibrational assignments of these isomers and to carry out meaningful force constant calculations for them. The N-N stretching frequency at 266 cm-1 for as-N2O3 and its stretching force constant of fNN = 0.57 mdyn/ both are characteristic of a very weak bond, although these values are higher than previously proposed. The N-O single bond stretching force constant for s-N2O3 was determined to be 3.61 mdyn/. 1983 American Chemical Society.
