Structure and IR Spectra of 3(5)-Aminopyrazoles and UV-Induced Tautomerization in Argon Matrix

The prototropic tautomerism in 3(5)-aminopyrazoles was investigated by matrix isolation infrared (IR) spectroscopy, supported by DFT(B3LYP)/6-311++G(d,p) calculations. In consonance with the experimental data, the calculations predict tautomer 3-aminopyrazole (3AP) to be more stable than the 5-aminopyrazole (5AP) tautomer (calculated energy difference: 10.7 kJ mol−1; Gibbs free energy difference: 9.8 kJ mol−1). The obtained matrix isolation IR spectra (in both argon and xenon matrices) were interpreted, and the observed bands were assigned to the tautomeric forms with help of vibrational calculations carried out at both harmonic and anharmonic levels. The matrix-isolated compound (in argon matrix) was then subjected to in situ broadband UV irradiation (λ > 235 nm), and the UV-induced transformations were followed by IR spectroscopy. Phototautomerization of the 3AP tautomer into the 5AP form was observed as the strongly prevalent reaction.

ИК спектроскопия высокого разрешения в низкотемпературных матрицах. Структура фундаментальных полос поглощения SiH-=SUB=-4-=/SUB=- в азотной и аргоновой матрицах

The features of high resolution IR spectra of the SiH4 molecule in N2 and Ar low-temperature matrices at 6.6-20 K were analyzed depending on experimental conditions. It was found, that in the nitrogen matrix in region of stretching vibration of 28SiH4 three narrow bands are observed, in the region of bending vibration (ν4) two bands are observed instead of one, which is explained by a change in the symmetry of the molecule from Td in the gas phase to C3v in solid nitrogen. In the argon matrix spectra change even more, where, in addition to narrow bands, the broad enough components are also recorded. The calculations of the SiH4 spectrum in the Ar matrix were performed based on the QM/MM approach, which confirm the reality of the change in the symmetry of the molecule as a result of its interaction with the matrix environment.