R. M. Pinto, A. Dias, G. Levita
Oct 10, 2012
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Influential Citations
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Journal
Journal of Molecular Structure
Abstract
Abstract The electronic structure, vibrational properties and pyrolysis behaviour of 3-azidopropionitrile (3APN, N3CH2CH2CN) are investigated using ultraviolet photoelectron spectroscopy (UVPES) and matrix-isolation infrared (IR) spectroscopy, supported by results from ab initio and DFT electronic structure calculations. 3APN is found to have an HOMO vertical ionisation energy (VIE) of 10.05 ± 0.02 eV and the strongest IR absorption bands located at 2173 and 1296 cm−1. Pyrolysis of the title compound revealed the presence of N2, HCN, CH3CN and ketenimine, H2C C NH, among the decomposition products, the latter behaving as a reaction intermediate. From G3 computational results, 3-iminopropionitrile, CN CH2CH NH, was found to be formed in competition with H2C N − CH2CN, through 160–180 kJ mol−1 energy barriers. On the basis of experimental evidence and G3 results, ketenimine is proposed as the dominant intermediate arising from further decomposition of both imine (CN CH2CH NH) and H2C N CH2CN compounds.