Molecular Structure, Vibrational Spectra and Photochemistry of 2-Methyl-2H-Tetrazol-5-Amine in Argon

GOMEZ ZAVAGLIA, ANDREA, I. REVA, L. FRIJA, L. CRISTIANO Y R. FAUSTO

JOURNAL OF PHYSICAL CHEMISTRY A

American Chemical Society

Lugar: 1100 Seventeenth Street, NW Suite 507 Washington, DC 20036-4632; Año: 2005 vol. 109 p. 7967 - 7976

1089-5639

In this work, the molecular structure, infrared spectrum and UV photochemistry of 2-methyl-2H-tetrazol-5-amine (2MTA) isolated in solid argon (10 K) were investigated. The experimental studies were supported by extensive DFT(B3LYP)/6-311++G(d,p) calculations. The infrared spectrum of matrix-isolated 2MTA was fully assigned and correlated with structural properties. Taking into consideration the observed frequency of the NH2 wagging mode, it is suggested that, in the matrixes, the amine group becomes slightly more planar than in the gas phase, due to matrix-packing effects. In situ UV irradiation (lambda > 235 nm) of the matrix-isolated 2MTA monomer is shown to induce three main primary photochemical processes: (1) tautomerization to mesoionic 3-methyl-1H-tetrazol-3-ium-5-aminide; (2) nitrogen elimination, with production of 1-methyl-1H-diazirene-3-amine; (3) ring cleavage leading to production of methyl azide and cyanamide. Following the primary photoproducts, secondary reactions were observed, leading to spectroscopic observation of methylenimine and isocyanidric acid.