Energy Decomposition Analysis of Lewis Acid/Base Adducts and Frustrated Lewis Pairs: The Use of EOrb/ESteric Ratios as a Reaction Parameter,Inorganic Chemistry

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Energy Decomposition Analysis of Lewis Acid/Base Adducts and Frustrated Lewis Pairs: The Use of EOrb/ESteric Ratios as a Reaction Parameter
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2021-07-30 , DOI: 10.1021/acs.inorgchem.1c00911
Elon A Ison ₁ , Joshua L Tubb ₁

Affiliation

The nature of bonding in classical adducts and frustrated Lewis pairs (FLPs) of oxorhenium and nitridorhenium complexes with B(C₆F₅)₃ was investigated computationally (B3PW91-D3). These studies have revealed that the primary noncovalent interaction (NCI) in the FLPs involves lone pair/π interactions between the terminal M≡X bond and the aromatic C₆F₅ ring in B(C₆F₅)₃. Energy decomposition analyses on classical adducts and FLPs reveal that these species can be defined by the ratio (E_Orb/E_Steric) of covalent-to-noncovalent contributions to the total interaction energy, E_Int. This type of analysis reveals that values for FLPs exist in a narrow range (1.2–2.5), with values for adducts significantly outside this range. The application of this method to other main-group combinations of Lewis acids and bases that have been shown to exhibit FLP reactivity yields similar results. These data suggest that similar NCIs are present in both transition-metal and main-group FLPs, especially where Lewis acids such as B(C₆F₅)₃ are utilized.

中文翻译：

路易斯酸/碱加合物和受阻路易斯对的能量分解分析：使用 EOrb/酯比作为反应参数

用计算方法研究了氧铼和氮化铼与 B(C ₆ F ₅ ) _{3 的}经典加合物和受挫路易斯对 (FLP) 中键合的性质(B3PW91-D3)。这些研究表明，FLP 中的主要非共价相互作用 (NCI) 涉及末端 M≡X 键和B(C ₆ F ₅ ) _{3 中}芳族 C ₆ F ₅环之间的孤对/π相互作用。经典加合物和 FLP 的能量分解分析表明，这些物种可以通过比率 ( E _Orb / E _Steric) 共价到非共价对总相互作用能E _{Int 的}贡献。这种类型的分析表明 FLP 的值存在于一个狭窄的范围内 (1.2-2.5)，加合物的值明显超出了这个范围。将此方法应用于已显示出 FLP 反应性的路易斯酸和碱的其他主要组合，会产生类似的结果。这些数据表明类似的 NCI 存在于过渡金属和主族 FLP 中，尤其是在使用路易斯酸如 B(C ₆ F ₅ ) _{3 的}情况下。

更新日期：2021-09-20

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