The mechanisms and regioselectivities of Fe(0)-catalyzed alkylation of aromatic compounds with alkenes were explored by DFT calculations. Our calculations show that these systems tend to undergo anti-Markovnikov addition. The influence of steric effects on the reaction mechanism has been investigated. The results indicate that the reaction is more likely to provide the linear product with dissociation of the 1PMe3 ligand. The reductive elimination is the rate-determining step of the whole process, such that the electrostatic interactions of the reaction site and the steric hindrance of the trimethylsilyl groups are favorable for the anti-Markovnikov rather than the Markovnikov addition pathway. Our calculations provide insights into the regioselective origin of the alkylation of aromatic compounds mediated by Fe(PMe3)4.

中文翻译：

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Fe(PMe3)4 催化芳烃与烯烃抗马尔科夫尼科夫加成反应制备线性烷基化产物的理论研究

通过 DFT 计算探索了 Fe(0) 催化芳族化合物与烯烃烷基化的机制和区域选择性。我们的计算表明，这些系统倾向于进行反马尔科夫尼科夫加法。研究了空间效应对反应机理的影响。结果表明该反应更有可能提供具有 1PMe3 配体解离的线性产物。还原消除是整个过程的限速步骤，因此反应位点的静电相互作用和三甲基甲硅烷基的空间位阻有利于反马尔科夫尼科夫而不是马尔科夫尼科夫加成途径。我们的计算提供了对 Fe(PMe3)4 介导的芳族化合物烷基化的区域选择性起源的见解。