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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Impact of Lewis acids on Diels-Alder reaction reactivity: A conceptual density functional theory study
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Impact of Lewis acids on Diels-Alder reaction reactivity: A conceptual density functional theory study

机译:路易斯酸对Diels-Alder反应活性的影响:概念性密度泛函理论研究

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摘要

Density functional theory (DFT) and conceptual/chemical DFT studies are carried out in this work for the normal electron demand Diels-Alder reaction between isoprene and acrolein to compare chemical reactivity and regioselectivity of the reactants in the absence and presence of Lewis acid (LA) catalysts. A cyclic coplanar structure of acrolein-LA complex has been observed and the natural bond orbital analysis has been employed to interpret the interaction between acrolein and LAs. Reactivity indices from frontier molecular orbital energies are proved to be adequate and efficient to evaluate the catalytic property of LAs. Linear relationships have been discovered among the bond order, bond length, catalytic activation, and chemical reactivity for the systems concerned. The validity and applicability of maximum hardness principle, minimum polarizability principle, and minimum electrophilicity principle are examined and discussed in the prediction of the major regioselective isomer and the preferred reaction pathway for the reactions in the present study.
机译:在这项工作中,针对异戊二烯和丙烯醛之间正常的电子需求Diels-Alder反应进行了密度泛函理论(DFT)和概念性/化学DFT研究,以比较在不存在和存在路易斯酸的情况下反应物的化学反应性和区域选择性(LA )催化剂。已观察到丙烯醛-LA复合物的环状共平面结构,并且已使用天然键轨道分析来解释丙烯醛和LA之间的相互作用。来自前沿分子轨道能量的反应性指数被证明是足够和有效的,以评估LAs的催化性能。在有关系统的键序,键长,催化活化和化学反应性之间发现了线性关系。在主要研究区域选择性异构体和预测反应的优选反应途径的预测中,研究并讨论了最大硬度原理,最小极化率原理和最小亲电原理的有效性和适用性。

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