Zhang Zheng-Feng, Su Ming-Der
Department of Applied Chemistry, National Chiayi University, Chiayi 60004, Taiwan.
Department of Medicinal and Applied Chemistry, Kaohsiung Medical University, Kaohsiung 80708, Taiwan.
Molecules. 2025 Apr 25;30(9):1905. doi: 10.3390/molecules30091905.
The [2 + 2] cycloaddition reactions of the heterocumulene () with the heavy imine-like molecule (G15 = Group 15 element) were examined using density functional theory (M06-2X-D3/def2-TZVP). The theoretical findings indicate that the doubly bonded Ge=G15 moiety in (LLGe=G15L) is characterized by electron-sharing bonding between the triplet LLGe and triplet G15-L fragments. All five Ge=G15-based heavy imine analogues readily undergo [2 + 2] cycloaddition reactions with . Energy decomposition analysis (EDA-NOCV) suggests that the [2 + 2] cycloaddition reaction between and involves a donor-acceptor (singlet-singlet) interaction instead of an electron-sharing (triplet-triplet) interaction. Frontier molecular orbital (FMO) theory and the energy decomposition analysis-natural orbitals for chemical valence (EDA-NOCV) findings emphasize that the key bonding interaction involves the occupied p-π orbital of and the vacant p-π* orbital of . Based on the activation strain model results, the activation barrier of the [2 + 2] cycloaddition reaction is predominantly controlled by the deformation energies of and .
使用密度泛函理论（M06 - 2X - D3/def2 - TZVP）研究了杂累积二烯（）与类重亚胺分子（G15 = 第15族元素）的[2 + 2]环加成反应。理论研究结果表明，（LLGe = G15L）中双键的Ge = G15部分的特征是三重态LLGe和三重态G15 - L片段之间的电子共享键。所有五种基于Ge = G15的重亚胺类似物都能与顺利进行[2 + 2]环加成反应。能量分解分析（EDA - NOCV）表明，与之间的[2 + 2]环加成反应涉及供体 - 受体（单重态 - 单重态）相互作用，而非电子共享（三重态 - 三重态）相互作用。前沿分子轨道（FMO）理论和能量分解分析 - 化学价自然轨道（EDA - NOCV）的研究结果强调，关键的键合相互作用涉及的占据p - π轨道和的空p - π*轨道。基于活化应变模型结果，[2 + 2]环加成反应的活化能垒主要由和的变形能控制。
