Molecular structure, vibrational spectra and photochemistry of 2-methyl-2H-tetrazol-5-amine in solid argon

被引:49
作者
Gómez-Zavaglia, A
Reva, ID
Frija, L
Cristiano, ML
Fausto, R [1 ]
机构
[1] Univ Coimbra, Dept Chem, P-3004535 Coimbra, Portugal
[2] Univ Buenos Aires, Fac Pharm & Biochem, RA-1113 Buenos Aires, DF, Argentina
[3] Univ Algarve, Dept Chem & Biochem, P-8005139 Faro, Portugal
关键词
D O I
10.1021/jp0517706
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
In this work, the molecular structure, infrared spectrum and UV photochemistry of 2-methyl-2H-tetrazol-5amine (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.
引用
收藏
页码:7967 / 7976
页数:10
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