Matrix-isolation FTIR study of azidoacetone and azidoacetonitrile

Abstract

Azidoacetonitrile (N 3 CH 2 CN) and azidoacetone (N 3 CH 2 COCH 3 ) were studied by matrix-isolation FTIR spectroscopy in solid neon, argon and nitrogen. The IR spectra calculated using the density fuctional theoretical method are discussed in comparison with the experimental data. Significant broadening of the recorded azide bands indicate an awkward fit of these compounds into the solid environment. The strongest absorption is observed for both compounds in the regions of asymmetric and symmetric stretches of the N 3 azide group. Strong band splittings in the N 3 asymmetric stretch region can be most likely explained by very strong Fermi resonances with the CN stretch and combinations and overtones of the numerous lower frequency vibrational modes.

Insights into the Photodecomposition of Azidomethyl Methyl Sulfide: A S2/S1 Conical Intersection on Nitrene Potential Energy Surfaces Leading to the Formation of S-Methyl-N-sulfenylmethanimine

“…The experimental spectrum reveals, six bands mentioned previously, strongest bands that extend from 2115 to 2134 cm –1 (Figure A). As it has been previously reported, the bands show asymmetric shapes, additional splitting, and an appreciable change in the intensities from matrix to matrix.…”

“…The experimental spectrum reveals, as previously mentioned six bands, strongest bands which are extending from 2115-2134 cm -1 (Figure 1A). As it has been previously reported, 30 the bands show asymmetric shapes, additional splitting, and an appreciable change in the intensities from matrix to matrix. as compared to Ar which could be related to low affinities of AMMS to form a welldefined local crystalline structure resulting in poorly defined sites, with a wide range of local geometries (matrix site effect, < 10 cm -1 , Figure S5).…”

Spectroscopic and Structural Studies of Difluorophosphoryl Azide F2P(O)N3, Difluorophosphoryl Isocyanate F2P(O)NCO, and Difluorophosphoric Acid Anhydride, F2(O)POP(O)F2

“…The “symmetric” stretch ( v 3 ) appears at 1280 cm −1 in the IR spectrum as a strong band, showing a comparable 15 N isotopic shift at the bridging nitrogen (Δ v ( 14/15 N b ) = 26.5 cm −1 ), and corresponds to a weak Raman band at 1283 cm −1 . Similar to the IR spectra of other matrix-isolated azides, the N 3 “antisymmetric” stretching band at 2206.2 cm −1 (Ar-matrix) is flanked by satellite bands (Figure , upper trace), which can probably be attributed to different matrix sites.…”

Insights into the Thermal and Photochemical Reaction Mechanisms of Azidoacetonitrile. Spectroscopic and MS‐CASPT2 Calculations

“…The present work is an experimental and theoretical study of both the photochemical as well as the thermal decomposition of azidoacetonitrile (AZN), a well‐known organic aliphatic azide, firstly prepared in 1932 by Freudenberg and later characterized by conventional FTIR spectroscopy in solid matrix as well as thermodynamically . In this work, experimental data dealing with the photochemical decom‐position of AZN are taken from the article of Boyer et al., while the experimental data concerning to the thermal decomposition of the azide were obtained by ourselves.…”