N=N Vibrational Frequencies and Fragmentation Patterns of Substituted 1-Aryl-3,3-Dialkyl-Triazenes: Comparison with other High-Nitrogen Compounds

Abstract

The influence of substitution pattern and electronic structure on the N=N stretching frequencies of compounds containing three to six linearly connected nitrogen atoms has been investigated by FT-IR and Raman spectroscopy. For a series of 1-phenyl-3,3-dialkyl-triazenes, Phe-N1=N2-N3 R2, shifts in the two valence vibrations of the triazeno group are studied with respect to the type and position of substituents at the aromatic ring, and for various alkyl substituents at N3. The N1=N2 stretching frequency is lowered by electron-withdrawing substituents at the aromatic ring; this effect is most pronounced for para-positioned substituents. A decrease in the N1=N2 bond order, and of the associated valence vibration, is also observed upon introduction of heavier N3-alkyl substituents, due to an inductive effect. Changes in vibrational frequencies are correlated with characteristic fragmentation patterns in the mass spectra of these compounds, where two degradation routes subsequent to ionization at the nitrogen atoms N1 and N2 have been observed. For the investigated pentazadiene derivatives, a weaker dependence of the N=N vibrational frequencies on the substituents is found. Mass spectra are interpreted in terms of two typical fragmentation pathways, involving a McLafferty rearrangement.