Ultra-violet absorption spectra and π-electron structures of nitromethane and the nitromethyl anion

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Abstract
The ultra-violet absorption spectrum of nitromethane was measured under various conditions. Besides the weak band at 270 mμ, a strong band, which may be regarded as due to the longest wavelength π→π* transition band, was observed at 198 mμ in the gaseous state. Further, the absorption spectrum of nitromethane was measured in aqueous solutions with several different ph values, and a strong band was observed at 233 mμ. From the fact that the pKa value evaluated on the basis of the ph dependence of the absorption intensity is equal to that obtained electrometrically, it was concluded that the 233 mμ band is to be ascribed to the nitromethyl anion (H2C-NO2). This band was found to shift to 238 mμ in alcoholic KOH solution. The π-electron structure of the anion was studied theoretically by taking into account configuration interaction in terms of the ground, charge transfer, and locally excited configurations. It is shown that the 233 mμ band of the anion may be interpreted as an intramolecular charge-transfer absorption involving a large electron transfer from CH2 - toward NO2. It is suggested that electron donating substituent groups like NH2, OH, and CH2 - should cause the 198 mμ band of the nitro group to shift toward shorter wavelengths, in marked contrast to the case of substituted benzene molecules like aniline and phenol.