Kimika Fakultatea, Euskal Herriko Unibertsitatea (UPV/EHU), P.K. 1072, 20080, Donostia, Euskadi, Spain.
Donostia International Physics Center (DIPC), 20018, Donostia, Euskadi, Spain.
Chemphyschem. 2019 Oct 2;20(19):2443-2450. doi: 10.1002/cphc.201900687. Epub 2019 Aug 30.
The tetravalent oxygen or sulphur centres, especially in H O and H S dications, were analysed experimentally and theoretically in various studies. Herein, we discuss stabilities of such centres in related H(CH ) O and H(CH ) S dications mediated by carborane superacid. The ωB97X-D/6-311++G(d,p) calculations were performed for a gas phase and for different solvents characterized by a wide range of dielectric constants for complexes of these dications with the conjugated base of H(CHB F ) carborane superacid, CHB F , which indicate that these complexes are linked by hydrogen bonds. The Quantum Theory of 'Atoms in Molecules' (QTAIM) approach is applied to characterize these interactions. DFT results show that tetravalent oxygen and sulphur structures are additionally stabilized by polar solvents.
四价氧或硫中心，特别是在 H2O 和 H2S 二阳离子中，在各种研究中得到了实验和理论的分析。在此，我们讨论了在由碳硼烷超强酸介导的相关 H(CH3)2O 和 H(CH3)2S 二阳离子中这些中心的稳定性。ωB97X-D/6-311++G(d,p)计算在气相和不同溶剂中进行，这些溶剂的介电常数范围很宽，用于这些二阳离子与 H(CHB F)5碳硼烷超强酸的共轭碱 CHB F5的配合物，这表明这些配合物通过氢键连接。应用“分子中的原子量子理论”（QTAIM）方法来表征这些相互作用。DFT 结果表明，四价氧和硫结构通过极性溶剂得到额外稳定。
