铝（I）介导的芳基碳-氟键氧化加成反应的机理特征：密度泛函理论计算的见解
Mechanistic Features in Al(I)-Mediated Oxidative Addition of Aryl C-F Bonds: Insights From Density Functional Theory Calculations.
作者信息
Zhang Xiangfei, Li Ping, Wang Binju, Cao Zexing
机构信息
State Key Laboratory of Physical Chemistry of Solid Surfaces, Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, and College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, China.
School of Chemistry and Pharmaceutical Engineering, Huanghuai University, Zhumadian, China.
出版信息
Front Chem. 2019 Sep 3;7:596. doi: 10.3389/fchem.2019.00596. eCollection 2019.
The oxidative addition of a range of robust aryl C-F bonds to a single Al(I) center supported by a (NacNac) bidentate ligand ((NacNac) = [ArNC(Me)CHC(Me)NAr] and Ar = 2,6- CH) have been explored by density functional theory calculations. Our calculations demonstrate that the Al(I) center-mediated C-F insertion generally proceeds the concerted mechanism that involve both the donation ( ) and back-donation ( ) interactions. In addition, the predicted free energy barriers for the C-F bond activation show good agreement with the experimental information available. Finally, the comparative studies show that B(I) is the most active among group III metals (B, Al, Ga), thus supplying a testable prediction for experiments.
通过密度泛函理论计算，研究了一系列由（NacNac）双齿配体（（NacNac） = [ArNC（Me）CHC（Me）NAr]且Ar = 2,6 - CH）支撑的稳定芳基C - F键与单个Al（I）中心的氧化加成反应。我们的计算表明，Al（I）中心介导的C - F插入反应通常通过涉及给予（ ）和反馈给予（ ）相互作用的协同机制进行。此外，预测的C - F键活化自由能垒与现有实验信息吻合良好。最后，比较研究表明，B（I）是第III族金属（B、Al、Ga）中活性最高的，从而为实验提供了一个可检验的预测。
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