Dynamic and static nature of activated interactions in transition states as elucidated by quantum theory of atoms‐in‐molecules dual functional analysis: A case of ligand exchange at the N of sulfonylimino‐λ3‐bromanes,International Journal of Quantum Chemistry

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Dynamic and static nature of activated interactions in transition states as elucidated by quantum theory of atoms‐in‐molecules dual functional analysis: A case of ligand exchange at the N of sulfonylimino‐λ3‐bromanes
International Journal of Quantum Chemistry ( IF 2.3 ) Pub Date : 2019-11-05 , DOI: 10.1002/qua.26073
Waro Nakanishi ₁ , Satoko Hayashi ₁ , Taro Nishide ₁ , Shota Otsuki ₁

Affiliation

A method to elucidate the dynamic and static natures of the activated interactions in transition states (TSs) is proposed using quantum theory of atoms‐in‐molecules (QTAIM) dual functional analysis (QTAIM‐DFA). The natures are determined for the ligand exchange at the N of sulfonylimino‐λ³‐bromanes, RBr‐*‐N(SO₂CF₃)‐*‐X′R′ (R, R′ = Me or Ph, X′ = Br′ or I′). Asterisks (*) emphasize the presence of bond critical points within the interactions in question. While data from the optimized structures of TSs correspond to the static nature, those from the perturbed and optimized structures represent the dynamic nature. The nature of the interactions in Br‐*‐N‐*‐X′ calculated with QTAIM‐DFA, using the perturbed structures generated using the normal coordinates for the imaginary frequencies (NIV), was very similar to that in trigonal bipyramidal adduct formation through charge transfer. The results with NIV were precisely the same as those obtained based on intrinsic reaction coordinate (IRC). The high applicability of QTAIM‐DFA is demonstrated when analyzing the activated interactions in TSs.

中文翻译：

过渡态中活化相互作用的动态和静态性质，如分子中原子的量子理论所阐明的双重功能分析：一个在磺酰氨基-λ3-溴的N处进行配体交换的案例

利用原子分子量子理论（QTAIM）双功能分析（QTAIM-DFA），提出了一种在过渡态（TSs）中阐明活化相互作用的动态和静态性质的方法。的性质被确定为在磺酰-λ的N的配位体交换^3个-bromanes，RBR - * - N（SO ₂ CF ₃）** X'R'（R，R'= Me或Ph，X'= Br'或I'）。星号（*）强调了所讨论的相互作用中键临界点的存在。虽然来自TS的优化结构的数据对应于静态性质，但是来自受扰和优化结构的数据则代表动态性质。通过QTAIM-DFA使用假想频率（NIV）的法向坐标生成的扰动结构，利用QTAIM-DFA计算的Br-*-N-*-X'中的相互作用的性质与通过生成双三角锥体加合物而形成的扰动结构非常相似电荷转移。NIV的结果与基于固有反应坐标（IRC）获得的结果完全相同。分析TS中激活的相互作用时，证明了QTAIM-DFA的高度适用性。

更新日期：2020-01-07

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