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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Photochemical isomerization reactions of cyanopyrroles: A theoretical study
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Photochemical isomerization reactions of cyanopyrroles: A theoretical study

机译：氰基吡咯的光化学异构化反应：理论研究

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摘要

The mechanisms of the photochemical isomerization reactions were investigated theoretically using a model system of 2-cyanopyrrole and 2-cyano-5-methylpyrrole with the CASSCF (eight-electron/seven-orbital active space) and MP2-CAS methods and the 6-311(d,p) basis set. The structures of the conical intersections, which play a decisive role in such phototranspositions, were obtained. The intermediates and transition structures of the ground state were also calculated to assist in providing a qualitative explanation of the reaction pathways. Our model investigations suggest that the preferred reaction route for the cyanopyrroles is as follows: reactant -> Franck-Condon region -> conical intersection -> photoproduct. In particular, the conical intersection mechanism found in this work gives a better explanation than the previously proposed internal cyclization-isomerization mechanism and supports the experimental observations. In addition, we suggest a simple p-pi orbital topology model, which can be used as a guide tool to predict the location at which conical intersections are likely to occur, as well as the conformations of the phototransposition products of various heterocycles.
机译：理论上使用2-氰基吡咯和2-氰基-5-甲基吡咯模型系统，采用CASSCF（八电子/七轨道活性空间），MP2-CAS方法和6-311方法对光化学异构化反应的机理进行了理论研究。 （d，p）基础集。获得了圆锥形相交的结构，其在这种光移位中起决定性作用。还计算了基态的中间体和过渡结构，以帮助提供对反应途径的定性解释。我们的模型研究表明，氰基吡咯的首选反应路线如下：反应物->弗兰克-康登区->圆锥形交叉点->光产物。特别是，在这项工作中发现的圆锥形相交机制比以前提出的内部环化-异构化机制提供了更好的解释，并支持了实验观察。此外，我们提出了一个简单的p-pi轨道拓扑模型，该模型可以用作指导工具，以预测可能发生圆锥形相交的位置以及各种杂环的光转座产物的构象。

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