Orozco-Valencia Ulises, Gázquez José L, Vela Alberto
Departamento de Química, Centro de Investigación y de Estudios Avanzados, Av. Instituto Politécnico Nacional 2508, 07360, Ciudad de México, México.
Departamento de Química, Universidad Autónoma Metropolitana-Iztapalapa, Av. San Rafael Atlixco 186, 09340, Ciudad de México, México.
J Mol Model. 2017 Jul;23(7):207. doi: 10.1007/s00894-017-3368-y. Epub 2017 Jun 20.
The net charge transfer process that occurs between two species, A and B, interacting with each other, may be decomposed into two processes: one in which A receives charge from B, which can be identified as the electrophilic channel for A or the nucleophilic channel for B, and a second in which A donates charge to B, which can be identified as the nucleophilic channel for A or the electrophilic channel for B. By determining the amount of charge associated with both processes through the minimization of the interaction energy associated with each case, the expressions for the amount of charge involved in each case can be expressed in terms of the directional chemical potentials and the hardnesses of the interacting species. The correlation between the charges obtained for the interaction between phosphine ligands of the type PRR'R'' and Ni, and the A carbonyl stretching frequency provides support for their interpretation as measures of the electrophilicity and nucleophilicity of a chemical species, and, at the same time, allows one to describe the donation and back-donation processes in terms of the density functional theory of chemical reactivity.
在相互作用的两个物种A和B之间发生的净电荷转移过程，可以分解为两个过程：一个过程是A从B接收电荷，这可以被确定为A的亲电通道或B的亲核通道；另一个过程是A向B捐赠电荷，这可以被确定为A的亲核通道或B的亲电通道。通过使与每种情况相关的相互作用能最小化来确定与这两个过程相关的电荷量，每种情况下涉及的电荷量表达式可以用相互作用物种的定向化学势和硬度来表示。对于PRR'R''型膦配体与Ni之间相互作用所获得的电荷与A羰基伸缩频率之间的相关性，为将它们解释为化学物种亲电性和亲核性的度量提供了支持，同时，也使得人们能够根据化学反应性的密度泛函理论来描述捐赠和反馈捐赠过程。
