Ahmed Sadia, Yang Wenhong, Ma Zhifeng, Sun Wen-Hua
Key laboratory of Engineering Plastics and Beijing National Laboratory for Molecular Science , Institute of Chemistry, Chinese Academy of Sciences , No. 2 North first Street , Zhongguancun, Beijing 100190 , China.
University of Chinese Academy of Sciences , Beijing 100049 , China.
J Phys Chem A. 2018 Dec 20;122(50):9637-9644. doi: 10.1021/acs.jpca.8b09121. Epub 2018 Dec 10.
The catalytic activities of α,α'-bisimino-2,3:5,6-bis(pentamethylene)pyridyl(Fe/Co) chloride analogue complexes are quantitatively investigated by the multiple linear regression analysis (MLRA) method. From the point of view of the electronic and steric effects, seven structural descriptors are selected and calculated, including the Hammett constant ( F), effective net charge ( Q), energy difference (Δ E), HOMO-LUMO energy gap (Δε, Δε), open cone angle (θ), and bite angle (β). In order to get better model, the fitting analyses are carried out by using the combinations of four, three, two, and single descriptors. The calculation results show quite good correlation results. By using two descriptors ( Q, β), the catalytic activities for both the Fe and Co complexes individually and also the variation between Fe and Co (Fe-Co) analogue system can be well predicted with correlation coefficient values over 0.934. It is found that the effective net charge ( Q) plays the dominant role in determining the catalytic activities for Fe and Co complexes. Furthermore, the lower values of catalytic activities in Co complexes are mainly attributed to the decreasing values of Q.
通过多元线性回归分析（MLRA）方法定量研究了α,α'-双亚氨基-2,3:5,6-双（亚戊基）吡啶基（铁/钴）氯化物类似物配合物的催化活性。从电子和空间效应的角度，选择并计算了七个结构描述符，包括哈米特常数（F）、有效净电荷（Q）、能量差（ΔE）、最高占据分子轨道-最低未占据分子轨道能隙（Δε、Δε）、开锥角（θ）和咬角（β）。为了获得更好的模型，通过使用四个、三个、两个和单个描述符的组合进行拟合分析。计算结果显示出相当好的相关性结果。通过使用两个描述符（Q，β），铁和钴配合物各自的催化活性以及铁和钴（Fe-Co）类似物体系之间的变化都可以得到很好的预测，相关系数值超过0.934。研究发现，有效净电荷（Q）在决定铁和钴配合物的催化活性方面起主导作用。此外，钴配合物中催化活性较低的值主要归因于Q值的降低。
