亲电性作为动力学行为的一种可能描述
Electrophilicity as a Possible Descriptor of the Kinetic Behaviour
摘要：
理解化学反应性描述符的精确性质是量子化学家最感兴趣的。在本调查中，已试图分析是否亲电性指数是一个可靠的描述动力学行为。Friedel-Crafts苄基化、乙酰化和苯甲酰化反应的相对实验速率与相应的计算亲电性值有很好的相关性。以各种取代乙烯的氯化反应和甲苯、氯苯的硝化反应为代表，分别研究了亲电加成反应和取代反应。相关性不是很好的评估，然而，通过去除一些数据点来显着改善，以表明亲电性是具有固有热力学信息的动力学量。实验和计算的活化能之间的相关性进行了研究，一些Markovnikov和反Markovnikov加成反应，并被证明是合理的。反应亲电性，局部亲电性和活化硬度一起使用，以提供一个透明的图片的反应速率以及芳香亲电取代反应的方向。强调了亲电性定义的模糊性。
英文摘要：
An understanding of the precise nature of a chemical reactivity descriptor is of utmost interest to quantum chemists. In the present investigation an attempt has been made to analyze whether the electrophilicity index is a reliable descriptor of the kinetic behaviour. Relative experimental rates of Friedel- Crafts benzylation, acetylation and benzoylation reactions correlate well with the corresponding calculated electrophilicity values. Chlorination of various substituted ethylenes and nitration of toluene and chlorobenzene are studied as representative examples of electrophilic addition and substitution reactions respectively. The correlation is not very good to assess that which, however, improves drastically by removing a few data points to show that the electrophilicity is a kinetic quantity with inherent thermodynamic information. The correlation between the experimental and the calculated activation energies is studied for some Markovnikov and anti-Markovnikov addition reactions and is turned out to be reasonably well. Reaction electrophilicity, local electrophilicity and activation hardness are used together to provide a transparent picture of reaction rates as well as the orientation of aromatic electrophilic substitution reactions. Ambiguity in the definition of the electrophilicity is highlighted.
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