• Bulletin of the Korean Chemical Society
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• 제35권7호
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• pp.2093-2096
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• 2014

2H-azirine, a less known acetonitrile isomer, is observed in matrix IR spectra from the precursor exposed to radiation from laser ablation of transition-metals. Its vibrational characteristics confirm the previous results, and those for the deuterated and $^{13}C$ substituted isotopomers are also newly reported. The weak absorptions are traced to the low production yield due to its high energy and low extinction constants. IRC computations reveal smooth inter-conversion between 2H-azirine and $CH_2NCH$, providing a rationale for the observed variation of their relative contents during photolysis.

• Bulletin of the Korean Chemical Society
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• 제34권5호
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• pp.1361-1365
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• 2013

The smallest ketenimine and hydrogen cyanide N-methylide ($CH_2CNH$ and $CH_2NCH$) are provided from the argon/acetonitrile matrix samples exposed to radiation from laser ablation of transition-metals. New infrared bands are observed in addition to better determination of the vibrational characteristics for the previously reported bands, and the $^{13}C$ substituted isotopomers ($^{13}{CH_2}^{13}CNH$ and $^{13}CH_2N^{13}CH$) are also generated. Density functional frequency calculations and the D and $^{13}C$ isotopic shifts substantiate the vibrational assignments. $CH_2CNH$ is probably produced through single-step conversion of $CH_3CN$, whereas $CH_2NCH$ through two-step conversion via 2H-azirine. Inter-conversions between these two products evidently do not occur during photolysis and annealing.