Kulsha Andrey V, Ragoyja Ekaterina G, Ivashkevich Oleg A
Chemical Department, Belarusian State University, 4 Nezavisimosti Avenue, 220030 Minsk, Republic of Belarus.
Laboratory for Chemistry of Condensed Systems, Research Institute for Physical Chemical Problems of the Belarusian State University, 14 Leningradskaya Street, 220006 Minsk, Republic of Belarus.
J Phys Chem A. 2022 Jun 16;126(23):3642-3652. doi: 10.1021/acs.jpca.2c00521. Epub 2022 Jun 3.
Brønsted superbases have wide applications in organic chemistry due to their ability to activate C-H bonds. The strongest neutral bases to date are substituted aminophosphazenes developed in the late 1980s by Reinhard Schwesinger. Since then, much effort has been expended to create even stronger neutral bases. In this article, the reasons for the instability of very basic compounds are investigated by means of high-level quantum-chemical calculations. Theoretical basicity limits are suggested for solutions as well as for the gas phase. A record-breaking superbase most likely to be synthesizable and stable at ambient conditions is proposed. Hexamethylphosphoramide is considered a reliable ionizing solvent for superbases.
布朗斯特超强碱由于能够活化碳氢键，在有机化学中有着广泛的应用。迄今为止，最强的中性碱是20世纪80年代末由莱因哈德·施韦辛格开发的取代氨基磷腈。从那时起，人们付出了很多努力来创造更强的中性碱。在本文中，通过高水平量子化学计算研究了极碱性化合物不稳定的原因。提出了溶液和气相的理论碱性极限。提出了一种在环境条件下最有可能合成且稳定的破纪录超强碱。六甲基磷酰胺被认为是超强碱的可靠电离溶剂。
