Chen Renhua, Lei Fengying, Jin Deze, Peng Ke, Liu Qingyu, Zhong Yeshuang, Hong Liang, Li Xiaolong, Zeng Zhu, Lu Tao
School of Basic Medical Sciences/School of Biology and Engineering, Guizhou Medical University, Guiyang 550025, China.
Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai 200433, China.
Molecules. 2024 Dec 5;29(23):5739. doi: 10.3390/molecules29235739.
Chalcogen bonds (ChBs) involving selenium have attracted substantial scholarly interest in past years owing to their fundamental roles in various chemical and biological fields. However, the effect of the valency state of the electron-deficient selenium atom on the characteristics of such ChBs remains unexplored. Herein, we comparatively studied the σ-hole-type Se∙∙∙O ChBs between SeF/SeF and a series of oxygen-bearing Lewis bases, including water, methanol, dimethyl ether, ethylene oxide, formaldehyde, acetaldehyde, acetone, and formic acid, using ab initio computations. The interaction energies of these chalcogen-bonded heterodimers vary from -5.25 to -11.16 kcal/mol. SeF participates in a shorter and stronger ChB than SeF for all the examined heterodimers. Such Se∙∙∙O ChBs are closed-shell interactions, exhibiting some covalent character for all the examined heterodimers, except for SeF∙∙∙water. Most of these chalcogen-bonded heterodimers are predominantly stabilized through orbital interactions between the lone pair of the O atom in Lewis bases and the σ*(Se-F) antibonding orbitals of Lewis acids. The back-transfer of charge from the lone pair of selenium into the σ* or π* antibonding orbitals of Lewis bases is also observed for all systems. Energy decomposition analysis reveals that the electrostatic component significantly stabilizes the targeted heterodimers, while the induction and dispersion contributions cannot be ignored.
近年来，涉及硒的硫族元素键（ChBs）因其在各种化学和生物领域的基础作用而引起了学术界的广泛关注。然而，缺电子硒原子的价态对这类硫族元素键特性的影响仍未得到探索。在此，我们使用从头算计算方法，对SeF/SeF与一系列含氧化合物路易斯碱（包括水、甲醇、二甲醚、环氧乙烷、甲醛、乙醛、丙酮和甲酸）之间的σ-空穴型Se∙∙∙O硫族元素键进行了比较研究。这些硫族元素键合异二聚体的相互作用能在-5.25至-11.16 kcal/mol之间变化。对于所有研究的异二聚体，SeF参与形成的硫族元素键比SeF短且强。这种Se∙∙∙O硫族元素键是闭壳层相互作用，除了SeF∙∙∙水之外，所有研究的异二聚体都表现出一定的共价特征。这些硫族元素键合异二聚体中的大多数主要通过路易斯碱中O原子的孤对电子与路易斯酸的σ*(Se-F)反键轨道之间的轨道相互作用而稳定。在所有体系中还观察到电荷从硒的孤对电子反向转移到路易斯碱的σ或π反键轨道。能量分解分析表明，静电成分显著稳定了目标异二聚体，而诱导和色散贡献也不可忽视。
