单硫代次膦酸异构体及质子转移异构化反应的理论研究

Theoretical Studies on the proton transfer isomerization of hypophosphorus acid

采用量子化学密度泛函B3LYP方法,在6—311++G**基组水平上全优化得到了硫代次磷酸的硫酮式和硫醇式两种构型异构体以及相应的对映异构体,同时对分子内质子转移异构化反应微观机理进行了理论分析.研究结果表明,硫酮式H2P(S)OH比硫醇式H2P(O)SH的能量低26.2 kJ/mol;质子转移异构化过程中形成一个四员环过渡态结构,与迁移原子H6无直接键连关系的其他构型参数在异构化过程几乎保持不变.

Theoretical studies on various geometrical structures of Hypophosphorous acid were carried out using DFT theoretical methods, at the B3LYP/6-311 ＋ ＋ G^＊＊ level. Intramolecular proton transfer isomerization has also been studied using the intrinsic reaction coordinate. The results show that thione isomer is stable with respect to thiol isomer from energetically, lower - 26. 2 kJ/mol corrected with zero point vibrational energy. The proton transfer reaction was characterized by the structure with a tetra-atomic ring,