The trapping reactions of carbene analogs G14F₂ (G14 = group 14 element) by the benzene-bridged B/P-Rea frustrated Lewis pair (FLPs) molecule are studied using density functional theory (B3LYP-D3(BJ)/def2-TZVP). Our theoretical investigations predict that only the CF₂ intermediate rather than other heavy carbene analogs can be trapped by the B/P-Rea FLP-type molecule. Energy decomposition analysis-natural orbitals for chemical valence (EDA-NOCV) analyses indicate that the bonding nature of the G14F₂ catching reactions by the B/P-Rea FLP-type molecule is a donor–acceptor (singlet–singlet) interaction rather than an electron-sharing (triplet–triplet) interaction. Moreover, EDA-NOCV and frontier molecular orbital (FMO) theory findings strongly suggest that the lone pair (LP) (P) → vacant p–π-orbital (G14F₂) interaction rather than the empty σ-orbital (B) ← sp²-σ-orbital (G14F₂) interaction plays a predominant role in establishing its bonding condition during the G14F₂ trapping reaction with the B/P-Rea FLP-associated molecule. Our activation strain model findings reveal that the atomic radius of the G14 element of G14F₂ plays a key role in determining the activation barrier of the G14F₂ trapping reactions by the benzene-bridged B/P-Rea FLP. The valence bond state correlation diagram (VBSCD) model developed by Shaik is used to rationalize the calculated results. The VBSCD findings demonstrate that in the present trapping reactions, the singlet triplet splitting of G14F₂ plays a significant role in influencing its reaction barrier and reaction enthalpy. Our theoretical results demonstrate that the relationship between the geometrical parameters of the transition states and the corresponding reaction free energy barriers agrees well with the findings based on the Hammond postulate.

中文翻译：

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苯桥联硼/磷基受挫路易斯对与二氟卡宾及其第 14 族类似物的捕获反应的反应性：理论研究

使用密度泛函理论 (B3LYP-D3(BJ)/def2-TZVP) 研究了苯桥接B/P-Rea受挫路易斯对 (FLPs) 分子对卡宾类似物G14F ₂ (G14 = 14 族元素) 的捕获反应. 我们的理论研究预测，只有CF ₂中间体而不是其他重卡宾类似物可以被B/P-Rea FLP 型分子捕获。能量分解分析-化学价的自然轨道 (EDA-NOCV) 分析表明G14F ₂的键合性质通过B/P-Rea捕捉反应FLP 型分子是供体-受体（单重态-单重态）相互作用，而不是电子共享（三重态-三重态）相互作用。此外，EDA-NOCV 和前沿分子轨道 (FMO) 理论研究结果强烈表明孤对 (LP) (P) → 空的 p-π-轨道 ( G14F ₂ ) 相互作用而不是空的 σ-轨道 (B) ← sp在与B/P-Rea FLP 相关分子的G14F ₂捕获反应期间， ² -σ-轨道 ( G14F ₂ ) 相互作用在建立其键合条件中起主要作用。我们的活化应变模型研究结果表明，G14F _{2的 G14 元素的原子半径}在确定苯桥接B/P-Rea FLP的G14F ₂捕获反应的活化势垒中起关键作用。Shaik开发的价键状态相关图（VBSCD）模型用于合理化计算结果。VBSCD研究结果表明，在目前的捕获反应中，G14F ₂的单重态三重态分裂在影响其反应势垒和反应焓方面起着重要作用。我们的理论结果表明，过渡态的几何参数与相应的反应自由能垒之间的关系与基于哈蒙德假设的发现非常吻合。