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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Experimental and Theoretical Investigation of the Pyrolysis Products of Iminodiacetonitrile, (N equivalent to CCH2)(2)NH
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Experimental and Theoretical Investigation of the Pyrolysis Products of Iminodiacetonitrile, (N equivalent to CCH2)(2)NH

机译：亚氨基二乙腈（N相当于CCH2）（2）NH的热解产物的实验和理论研究

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摘要

The gas-phase FTIR study of the pyrolysis products of iminodiacetonitrile, (N CCH2)(2)NH has revealed the existence of C-cyanomethanimine, N CCH NH, and ketenimine, CH2=C=NH. The former has two isomers: Z and E; while the later readily taumerizes to acetonitrile, CH3C N. A trapping/revaporization system has been used to purify C-cyanomethanimine. The analysis of the rotational structures of the IR medium resolution C-type CNH bend, nu(6), and C-N torsional mode, nu(10), has led to a conformational characterization of these isomers. The Z-isomer was shown to be the major product. This conjecture was supported by ab initio MO calculations that confirmed the relative total energy stability of the Z-isomer over its E-counterpart by 0.173 to 2.326 kJ/mol. The K values indicated that the equilibrium concentration of Z-C-cyanomethanimine amounts to up to three times that of E-C-cyanomethanimine. A further investigation using NBO technique proved the predilection of the Z-isomer. In addition it relates its provenance of preference to the remote n(N6) -> sigma*(C4N5) interaction that stabilized it by 1.10 kcal/mol. A thorough theoretical investigation of the tautomerization reaction between ketenimine and acetonitrile will be published in a separate contribution.
机译：亚氨基二乙腈（N CCH2）（2）NH的热解产物的气相FTIR研究表明，存在C-氰基甲亚胺，N CCH NH和酮亚胺，CH2 = C = NH。前者有两个异构体：Z和E;后来又容易变成乙腈CH3CN。红外中分辨率C型CNH弯曲nu（6）和C-N扭转模式nu（10）的旋转结构分析导致这些异构体的构象表征。 Z-异构体被证明是主要产物。该推测得到了从头算MO的支持，该计算从零开始确认Z异构体相对于其电子对角的相对总能量稳定性为0.173至2.326 kJ / mol。 K值表明Z-C-氰基甲基亚胺的平衡浓度高达E-C-氰基甲基亚胺的平衡浓度的三倍。使用NBO技术的进一步研究证明了Z-异构体的偏爱。另外，它将其优先来源与远程n（N6）→sigma *（C4N5）相互作用相关，该相互作用使它稳定1.10 kcal / mol。将单独发表关于酮亚胺和乙腈之间互变异构反应的详尽理论研究。

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