Brzeski Jakub
Faculty of Chemistry, University of Gdańsk, Wita Stwosza 63, Gdańsk 80-308, Poland.
J Phys Chem A. 2024 Jun 27;128(25):5009-5020. doi: 10.1021/acs.jpca.4c02663. Epub 2024 Jun 13.
The abundance of XIII group element compounds in science and industry together with their electron-deficient character gives rise to their influence on properties of the systems they interact with. This paper is an attempt to assess the strength, nature, and effect of formation of a triel bond on acidity. A wide set of Brønsted acids among others comprising hydrocarbons, halogen hydrides, and amines bonded with B, Al, and Ga trifluorides forming HX/TF was selected for the research. Various computational approaches (e.g., MP2, GFN2-xTB, SAPT2 + 3(CCD)δ, quantum theory of atoms in molecules analysis, and density overlap regions indicator) are used to describe the triel-bonded systems. Among other things, it was found that the electrostatics may not be the dominant contribution to the triel binding in some cases. Additionally, it was established that even weak Brønsted acids such as CH or H may be superacidic if bonded to a Lewis acid (TF) that is strong enough. The calculations indicate a significant covalent character of some of the studied HX/TF triel-bonded systems. Moreover, the effect of solvation of HX with TF as well as that of the reverse process on the acidity of the resulting system is thoroughly described.
科学和工业中第13族元素化合物的丰富性及其缺电子特性，使其对与之相互作用的体系的性质产生影响。本文旨在评估三族元素键对酸度的形成强度、性质和影响。研究选用了一系列广泛的布朗斯特酸，包括与硼、铝和镓的三氟化物形成HX/TF的碳氢化合物、卤化氢和胺。使用了各种计算方法（如MP2、GFN2-xTB、SAPT2 + 3(CCD)δ、分子中原子的量子理论分析和密度重叠区域指示器）来描述三族元素键合体系。研究发现，在某些情况下，静电作用可能不是三族元素键合的主要贡献。此外，研究还确定，即使是像CH或H这样的弱酸，如果与足够强的路易斯酸（TF）结合，也可能具有超强酸性。计算结果表明，一些研究的HX/TF三族元素键合体系具有显著的共价特性。此外，还详细描述了HX与TF的溶剂化作用以及相反过程对所得体系酸度的影响。
