一组不寻常开环电环反应的环选择性研究:通过自然键轨道分析和分子中原子的量子理论确定电子键结构,并通过键反应性描述符分析电子反应机理

IF 2.3 3区 化学 Q3 CHEMISTRY, PHYSICAL International Journal of Quantum Chemistry Pub Date : 2024-10-07 DOI:10.1002/qua.27494
Jesús Sánchez-Márquez, Alejandro Morales-Bayuelo
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引用次数: 0

摘要

在这项工作中,我们研究了一组不寻常的开环电环反应的转折选择性,这些反应既没有成功地用基于轨道对称性的模型来合理解释,也没有用立体阻碍来解释。首先,我们获得了相应的过渡态,并验证了与这些过渡态相关的固有反应坐标与所研究反应的反应物和产物是一致的。这样,我们就可以从理论上计算反应壁垒(及其相应的热修正),并将其与相应的实验值进行比较。第二步,我们利用自然键轨道分析和分子中原子量子理论的方法分析了电子键结构,寻找可能显著稳定过渡态的相互作用。最后,我们利用一个最新模型分析了反应性,该模型使我们能够计算相应的键反应性描述符。
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Study of the Torquoselectivity of a Set of Unusual Ring-Opening Electrocyclic Reactions: Determination of the Electronic Bonding Structure Through the Methodologies of Natural Bond Orbital Analysis and Quantum Theory of Atoms in Molecules, and Analysis of the Electronic Reaction Mechanism Through Bond Reactivity Descriptors

In this work, we have studied the torquoselectivity of a set of unusual ring-opening electrocyclic reactions that have not been successfully rationalized using models based on orbital symmetry nor have they been explained by steric hindrance. Firstly, the corresponding transition states have been obtained, and it has been verified that the intrinsic reaction coordinates associated with these transition states are consistent with the reactants and products of the reactions studied. This has allowed us to theoretically calculate the reaction barriers (with their corresponding thermal corrections) and compare them with the corresponding experimental values. In a second step, we have analyzed the electronic bonding structure using the methodologies of Natural Bond Orbital Analysis and Quantum Theory of Atoms in Molecules, searching for interactions that may significantly stabilize the transition states. Finally, we have analyzed the reactivity using a recent model that has allowed us to calculate the corresponding bond reactivity descriptors.

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来源期刊
International Journal of Quantum Chemistry
International Journal of Quantum Chemistry 化学-数学跨学科应用
CiteScore
4.70
自引率
4.50%
发文量
185
审稿时长
2 months
期刊介绍: Since its first formulation quantum chemistry has provided the conceptual and terminological framework necessary to understand atoms, molecules and the condensed matter. Over the past decades synergistic advances in the methodological developments, software and hardware have transformed quantum chemistry in a truly interdisciplinary science that has expanded beyond its traditional core of molecular sciences to fields as diverse as chemistry and catalysis, biophysics, nanotechnology and material science.
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