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首页> 外文期刊>RSC Advances >DFT investigation of hydrogen atom-abstraction reactions of NHC-boranes by various carbon-centered radicals: barriers and correlation analyses
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DFT investigation of hydrogen atom-abstraction reactions of NHC-boranes by various carbon-centered radicals: barriers and correlation analyses

机译：各种碳源基团NHC-硼酸硼氢原子抽象反应的DFT研究：屏障和相关分析

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In this study, we employed a quantum-mechanical computational method to investigate the hydrogen-atom abstraction reactions of two nitrogen heterocyclic carbene boranes (NHC-boranes), NHC-BH _(3) and NHC-BH _(2) CN, by a series of carbon-centered radicals bearing various substituents. We explored the degree of correlation of the activation and free energy barriers to their components. Furthermore, we also investigated the effects of the radical and substituent sizes, nucleophilicity/electrophilicity indices, and the spin density distribution of the radical reactants on the three fundamental barriers and the thermal contribution of the reaction energy to the kinetic barrier. Using the generated data, we assessed the abilities of the various radical reactants to abstract the hydrogen atom from NHC-boranes. Further, we performed a similar analysis after dividing those radical reactants into four groups, which were classified based on the dominant factor affecting their electronic density distribution, which involves the inductive effect, conjugation, hyperconjugation, and the feedback of lone-pair electrons. The results and conclusions of this investigation not only provide insight into the relationships between some of the key kinetic and thermodynamic parameters, which is useful for understanding the dynamics of such hydrogen-abstraction reactions, but also provide information for selecting suitable radical reactants for further experimental investigations.
机译：在这项研究中，我们采用量子机械计算方法研究了两种氮杂环硼烷硼（NHC-硼烷），NHC-BH_（3）和NHC-BH _（2）CN的氢原子抽象反应，通过一系列碳源于各种取代基的碳素为基础。我们探讨了激活和自由能屏障对其组件的相关程度。此外，我们还研究了激进和取代基尺寸，亲核/亲电子指数的影响，亲核性/电泳指数以及自由基反应物的旋转密度分布对三个基本屏障和反应能对动力学屏障的热贡献。使用所产生的数据，我们评估了各种激进反应物的能力，以摘要来自NHC-硼烷的氢原子。此外，在将这些自由基反应物分成四组之后，我们进行了类似的分析，该分析基于影响其电子密度分布的主导因素，这涉及诱导效果，缀合，超强谐波和唯一对电子的反馈。该研究的结果和结论不仅可以深入了解一些关键动力学和热力学参数之间的关系，这对于了解这种氢气抽象反应的动态是有用的，而且还提供用于选择合适的自由基反应物以进行进一步实验的信息调查。

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