Energy Decomposition Analysis of Lewis Acid/Base Adducts and Frustrated Lewis Pairs: The Use of E Orb / E Steric Ratios as a Reaction Parameter
Energy Decomposition Analysis of Lewis Acid/Base Adducts and Frustrated Lewis Pairs: The Use of E Orb / E Steric Ratios as a Reaction Parameter
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路易斯酸/碱加合物和受抑路易斯对的能量分解分析：使用 E Orb / E 空间比作为反应参数
DOI：
10.1021/acs.inorgchem.1c00911
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发表时间：
2021
影响因子：
4.6
通讯作者：
Tubb, Joshua L.
中科院分区：
文献类型：
--
作者：
Ison, Elon A.;Tubb, Joshua L.
计算研究了氧铼和氮铼与B（C6 F5）3的经典加合物和阻挫刘易斯对（FLP）的成键性质（B3 PW 91-D3）。这些研究揭示了FLP中的主要非共价相互作用（NCI）涉及B（C6 F5）3中的末端M-X键和芳香族C6 F5环之间的孤对/π相互作用。经典的加合物和FLP的能量分解分析表明，这些物种可以定义的比率（EOrb/Esteric）的共价到非共价的贡献的总相互作用能，EInt。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这个范围。将该方法应用于已显示出FLP反应性的刘易斯酸和碱的其它主族组合产生类似的结果。这些数据表明，类似的NCIs存在于过渡金属和主族FLP中，特别是在使用刘易斯酸如B（C6 F5）3的情况下。
The nature of bonding in classical adducts and frustrated Lewis pairs (FLPs) of oxorhenium and nitridorhenium complexes with B(C6F5)3was 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 C6F5ring in B(C6F5)3. Energy decomposition analyses on classical adducts and FLPs reveal that these species can be defined by the ratio (EOrb/ESteric) of covalent-to-noncovalent contributions to the total interaction energy,EInt. 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)3are utilized.