Ammonia easily reacts on cyanoacetylene in the gas phase or in a solvent to form the Z- and E-isomers of aminoacrylonitrile (3-amino-2-propenenitrile, 2). This kinetically stable enamine presents interest for its possible presence in the interstellar medium, the comets, the atmospheres of Planets including the Primitive Earth, and from a theoretical point of view. B3LYP/6-311+G(3df,2p) and G2 calculations indicate that the imine isomer is significantly less stable than the enamine 2. DFT and G2 calculations indicate that the Z-isomer of compound 2 lies ca. 8.0 kJ mol(-1) lower in energy than the E-isomer. The infrared spectra of the aminoacrylonitrile, in both the gas and condensed phases were recorded in the range 500-4000 cm(-1). Consistent with the theoretical calculations, the imine and the E-isomer of the enamine have never been detected in the infrared spectrum of a gaseous sample and only the Z-isomer has been observed. With a neat sample in the condensed phase, IR spectra of a 1:1 and 20:1/Z:E mixtures were recorded. The comparison of these data with the spectrum of the Z-isomer in the gas phase allowed us to deduce the IR spectrum of the E-isomer. The E-Z isomerization takes place through a torsion around the C=C bond. A possible mechanism involving a previous enamine-imine tautomerism must be discarded because it implies a much larger barrier than the direct isomerization process. Consistently, the presence of a deuterium atom has not been observed on the sp2 carbon of the products of distillation of a 1:1/E:Z mixture of the NCCH=CHND2.

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