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首页> 外文期刊>Chemistry: A European journal >Mechanistic investigations on the photoisomerization reactions of 1,2-dihydro-1,2-azaborine
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Mechanistic investigations on the photoisomerization reactions of 1,2-dihydro-1,2-azaborine

机译：1,2-二氢-1，2-天麻黄素光致异构化反应的机理研究

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The mechanisms of the photochemical isomerization reactions were investigated theoretically by using a model system of 1,2-dihydro-1,2-azaborine with the CAS(6,6)/6-311G(d,p) and MP2-CAS-(6,6)/6-311++G(3df,3pd)//CAS(6,6)/6- 311G(d,p) methods. Three reaction pathways, which lead to three kinds of photoisomers, have been examined. The structures of the conical intersections, which play a decisive role in such photorearrangements, were obtained. The thermal (or dark) reactions of the reactant species have also been examined by using the same level of theory to assist in providing a qualitative explanation of the reaction pathways. The model investigations suggest that the preferred reaction route for 1,2-dihydro-1,2-azaborine, which leads to the Dewar 1,2-dihydro-1,2-azaborine photoproduct, is as follows: reactant→Franck- Condon region→conical intersection→photoproduct. The results obtained allow a number of predictions to be made. Photoisomer pathways: The ground- and ~1(ππ*)-state potential energy surfaces of 1,2-dihydro-1,2-azaborine species were studied with CAS/6-311G(d,p) and MP2-CAS/6-311++G(3df,3pd) methods. Three reaction pathways were examined (see figure). The theoretical results are in good agreement with the available experimental observations for the photorearrangement reactions under singlet direct or sensitized irradiation.
机译：理论上，使用CAS（6,6）/ 6-311G（d，p）和MP2-CAS-（1,2-dihydro-1,2-azaborine）模型系统，对光化学异构化反应的机理进行了理论研究。 6,6）/ 6-311 ++ G（3df，3pd）// CAS（6,6）/ 6- 311G（d，p）方法。已经研究了导致三种光异构体的三个反应途径。获得了在这种光重排中起决定性作用的圆锥形相交的结构。还通过使用相同水平的理论来检查反应物物种的热（或暗）反应，以帮助提供反应路径的定性解释。模型研究表明，导致杜瓦1,2-二氢-1,2-天青碱光产物的1,2-二氢-1，2-天青碱的优选反应路线如下：反应物→弗朗克-康登区→锥形相交→照相产品。获得的结果使得可以做出许多预测。光异构体途径：用CAS / 6-311G（d，p）和MP2-CAS / 6研究了1,2-二氢-1,2-氮杂aboborine物种的基态和〜1（ππ*）-态势能表面-311 ++ G（3df，3pd）方法。检查了三个反应途径（见图）。理论结果与单线直接或敏化辐射下光重排反应的可用实验观察结果非常吻合。

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