Journal of Chemical Sciences ( IF 1.7 ) Pub Date : 2022-01-25 , DOI: 10.1007/s12039-021-02010-4
Manas Ghara 1 , Prasenjit Das 1 , Pratim Kumar Chattaraj 1, 2 , Santanab Giri 3
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The activation of the C-F bond in 1-fluorobutane, 1, 1-difluorobutane and 1, 1, 1-trifluorobutane by some frustrated Lewis pair (FLP) has been assessed by DFT based computational study. The FLPs are constructed from lutidine Lewis base in association with either B(C6F5)3 or Al(C6F5)3. Thermodynamics and kinetics of the reactions are studied, which reveals the concerning bond activation mediated by the Al(C6F5)3/lutidine FLP is more favourable than the analogous reactions mediated by the B(C6F5)3/lutidine pair. Therefore, the Al(C6F5)3 acid is superior to the B(C6F5)3 acid to construct an effective FLP for some unusual bond activation. The EDA-NOCV study together with the WBI calculation reveals the C-F bond activation in the studied systems takes place by the cooperative action of the FLP partners. The activation strain model reveals the strain energy of the reactants to reach the transition state (TS) rather than the interaction energy at the TS is the decisive factor to the TS barrier height of the concerned reactions.
Graphical abstract
The activation of C-F bond in 1-fluorobutane, 1, 1-difluorobutane and 1, 1, 1-trifluorobutane by B(C6F5)3/lutidine and Al(C6F5)3/lutidine pairs has been assessed computationally. The Al(C6F5)3/lutidine pair is superior to the B(C6F5)3/lutidine pairs for such unusual bond activation as revealed by this study.
中文翻译：
B(C6F5)3/lutidine 和 Al(C6F5)3/lutidine 受挫的 Lewis 对可能激活 CF 键：计算机研究
已通过基于 DFT 的计算研究评估了一些受挫路易斯对 (FLP) 对 1-氟丁烷、1, 1-二氟丁烷和 1, 1, 1-三氟丁烷中 CF 键的活化作用。FLP由二甲基吡啶路易斯碱与B(C 6 F 5 ) 3或Al(C 6 F 5 ) 3结合构成。研究了反应的热力学和动力学，揭示了由 Al(C 6 F 5 ) 3 /二甲基吡啶 FLP 介导的相关键活化比由 B(C 6 F 5 ) 3 /二甲基吡啶对介导的类似反应更有利. 因此，Al(C6 F 5 ) 3酸优于B(C 6 F 5 ) 3酸以构建有效的FLP，用于一些不寻常的键活化。EDA-NOCV 研究与 WBI 计算一起揭示了所研究系统中的 CF 键激活是由 FLP 合作伙伴的合作行为发生的。活化应变模型揭示了反应物达到过渡态（TS）的应变能而不是TS处的相互作用能是相关反应的TS势垒高度的决定性因素。
图形概要
B(C 6 F 5 ) 3 /二甲基吡啶和Al(C 6 F 5 ) 3 /二甲基吡啶对对1-氟丁烷、1, 1-二氟丁烷和1, 1, 1-三氟丁烷中CF键的活化已通过计算评估. Al(C 6 F 5 ) 3 /二甲基吡啶对在这种不寻常的键活化方面优于B(C 6 F 5 ) 3 /二甲基吡啶对，如本研究所示。
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