Liu Shubin, Rong Chunying, Lu Tian
Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research (Ministry of Education of China), Synergetic Innovation Center for Quantum Effects and Applications (SICQEA), College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha, Hunan 410081, China and Research Computing Center, University of North Carolina, Chapel Hill, North Carolina 27599-3420, USA.
Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research (Ministry of Education of China), Synergetic Innovation Center for Quantum Effects and Applications (SICQEA), College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha, Hunan 410081, China.
Phys Chem Chem Phys. 2017 Jan 4;19(2):1496-1503. doi: 10.1039/c6cp06376d.
One of the main tasks of theoretical chemistry is to rationalize computational results with chemical insights. Key concepts of such nature include nucleophilicity, electrophilicity, regioselectivity, and stereoselectivity. While computational tools are available to predict barrier heights and other reactivity properties with acceptable accuracy, a conceptual framework to appreciate above quantities is still lacking. In this work, we introduce the electronic force as the fundamental driving force of chemical processes to understand and predict molecular reactivity. It has three components but only two are independent. These forces, electrostatic and steric, can be employed as reliable descriptors for nucleophilic and electrophilic regioselectivity and stereoselectivity. The advantages of using these forces to evaluate molecular reactivity are that electrophilic and nucleophilic attacks are featured by distinct characteristics in the electrostatic force and no knowledge of quantum effects included in the kinetic and exchange-correlation energies is required. Examples are provided to highlight the validity and general applicability of these reactivity descriptors. Possible applications in ambident reactivity, σ and π holes, frustrated Lewis pairs, and stereoselective reactions are also included in this work.
理论化学的主要任务之一是用化学见解使计算结果合理化。这类性质的关键概念包括亲核性、亲电性、区域选择性和立体选择性。虽然有计算工具可用于以可接受的精度预测势垒高度和其他反应性质，但仍缺乏一个理解上述量的概念框架。在这项工作中，我们引入电子力作为化学过程的基本驱动力，以理解和预测分子反应性。它有三个分量，但只有两个是独立的。这些力，即静电力和空间力，可作为亲核和亲电区域选择性及立体选择性的可靠描述符。使用这些力评估分子反应性的优点在于，亲电和亲核攻击在静电力方面具有明显特征，并且不需要了解动力学和交换相关能量中包含的量子效应。文中提供了示例以突出这些反应性描述符的有效性和普遍适用性。这项工作还包括在两可亲核反应、σ和π空穴、受阻路易斯酸碱对以及立体选择性反应中的可能应用。
