Research Computing Center, University of North Carolina , Chapel Hill, North Carolina 27599-3420, United States.
J Phys Chem A. 2014 May 22;118(20):3698-704. doi: 10.1021/jp5032702. Epub 2014 May 7.
Electrophilic and nucleophilic reactions are important chemical transformations involving charge acceptance and donation, so chemical intuition suggests that atomic charges should be a reliable descriptor to determine electrophilicity, nucleophilicity, and regioselectivity. Nevertheless, no such theoretical framework has been established as of yet. Herein, we report that the Hirshfeld charge can be used for such purposes. We justify this usage by showing that it results from the Information Conservation Principle. This principle not only decides where electrophilic and nucleophilic attacks will preferably occur but also dictates the amount of the Hirshfeld charge distribution, which, as we will show here, remarkably strongly correlates with experimental scales of both electrophilicity and nucleophilicity.
亲电和亲核反应是涉及电荷接受和捐赠的重要化学转化，因此化学直觉表明原子电荷应该是确定亲电性、亲核性和区域选择性的可靠描述符。然而，到目前为止，还没有建立这样的理论框架。在这里，我们报告说，Hirshfeld 电荷可用于此类目的。我们通过证明它是由信息守恒原理产生的来证明这种用法的合理性。该原理不仅决定了亲电和亲核攻击将优先发生的位置，而且还决定了 Hirshfeld 电荷分布的数量，正如我们将在这里展示的那样，它与亲电性和亲核性的实验尺度非常强烈地相关。
