Rational Development of a Metal-Free Bifunctional System for the C−H Activation of Methane: A Density Functional Theory Investigation,ChemPhysChem

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Rational Development of a Metal-Free Bifunctional System for the C−H Activation of Methane: A Density Functional Theory Investigation
ChemPhysChem ( IF 2.3 ) Pub Date : 2021-07-26 , DOI: 10.1002/cphc.202100527
Damien Mahaut ₁ , Aurélien Chardon ₁ , Loïc Mineur ₁ , Guillaume Berionni ₁ , Benoît Champagne ₁

Affiliation

The activation or heterolytic splitting of methane, a challenging substrate usually restricted to transition metals, has so far proven elusive in experimental frustrated Lewis pair (FLP) chemistry. In this article, we demonstrate, using density functional theory (DFT), that 1-aza-9-boratriptycene is a conceptually simple intramolecular FLP for the activation of methane. Systematic comparison with other FLP systems allows to gain insight into their reactivity with methane. The thermodynamics and kinetics of methane activation are interpreted by referring to the analysis of the natural charges and by employing the distortion-interaction/activation strain (DIAS) model. These showed that the nature of the Lewis base influences the selectivity over the reaction pathway, with N Lewis bases favoring the deprotonation mechanism and P bases the hydride abstraction one. The lower barrier of activation for 1-aza-9-boratriptycene and the higher products stability are due to a better interaction energy than its counterparts, itself due to electrostatic interactions with the methane moiety, favorable orbital overlaps allowed by the side-attack, and space proximity between the B and N atoms.

中文翻译：

用于甲烷 C−H 活化的无金属双功能系统的合理开发：密度泛函理论研究

甲烷的活化或异裂分裂是一种通常仅限于过渡金属的具有挑战性的底物，迄今为止在实验受挫路易斯对 (FLP) 化学中证明是难以捉摸的。在本文中，我们使用密度泛函理论 (DFT) 证明 1-aza-9-boratriptycene 是一种概念上简单的用于活化甲烷的分子内 FLP。与其他 FLP 系统进行系统比较，可以深入了解它们与甲烷的反应性。甲烷活化的热力学和动力学通过参考自然电荷的分析并采用变形-相互作用/活化应变（DIAS）模型来解释。这些表明路易斯碱的性质影响了反应途径的选择性，N 路易斯碱有利于去质子化机制，P 碱是氢化物提取机制。1-aza-9-boratriptycene 较低的活化能垒和较高的产物稳定性是由于比其对应物更好的相互作用能，其本身是由于与甲烷部分的静电相互作用，侧向攻击允许的有利轨道重叠，以及B 和 N 原子之间的空间接近度。

更新日期：2021-07-26

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