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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Theoretical Study of Reactivities in Electrophilic Aromatic Substitution Reactions: Reactive Hybrid Orbital Analysis
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Theoretical Study of Reactivities in Electrophilic Aromatic Substitution Reactions: Reactive Hybrid Orbital Analysis

机译：亲电取代反应中反应性的理论研究：反应性混合轨道分析

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摘要

Orbital interactions in electrophilic aromatic substitution reactions of anisol, nitrobenzene, and some other analogues were studied. A single frontier orbital (FO), i.e., the HOMO of substituted benzenes, particularly of nitrobenzene, does not account for the regioselectivities of the reaction. We first applied configuration analysis to identify the relative importance of orbital interactions between an electrophile (H~+ in this work) and the substituted benzenes. We herein define the reactive hybrid orbital (RHO) method for measuring the reactivity of each carbon atom of substituted benzene. An RHO is made by combining all occupied molecular orbitals properly so that the reactivity index for a reaction center, which is similar to superdelocalizability, is maximized. The RHO reactivity indices, λ_(oc), ρ_(oc), and ρ'_(oc), were shown to predict correctly the experimentally observed regioselectivity and reactivity in the electrophilic aromatic substitution reactions of anisol, nitrobenzene, and other monosubstituted benzenes. Moreover, it was shown that the RHO values for carbon atoms in a polycyclic aromatic hydrocarbon are in good agreement with experimentally determined partial rate factors.
机译：研究了苯甲醚，硝基苯和其他一些类似物的亲电芳香取代反应中的轨道相互作用。单个前沿轨道（FO），即取代的苯，特别是硝基苯的HOMO，不能解释反应的区域选择性。我们首先应用构型分析来确定亲电体（在这项工作中为H〜+）与取代苯之间的轨道相互作用的相对重要性。我们在本文中定义了反应性杂化轨道（RHO）方法，用于测量取代苯的每个碳原子的反应性。通过适当地合并所有占据的分子轨道来制备RHO，以使反应中心的反应指数（与超离域性相似）最大化。显示RHO反应性指数λ_（oc），ρ_（oc）和ρ'_（oc）可以正确预测在苯甲醚，硝基苯和其他单取代苯的亲电芳香取代反应中实验观察到的区域选择性和反应性。此外，已经表明，多环芳烃中碳原子的RHO值与实验确定的部分速率因子高度吻合。

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