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

作　　者：吴东兵[1] 王渭娜[2] 赵飞[2] 王文亮[2] 

机构地区：[1]延安大学化学与化工学院,陕西延安716000 [2]陕西师范大学化学与材料科学学院,陕西西安710062

出　　处：《陕西师范大学学报（自然科学版）》2008年第1期61-64,共4页Journal of Shaanxi Normal University：Natural Science Edition

基　　金：陕西省自然科学基金资助项目(2006B12)

摘　　要：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,

关 键 词：单硫代次膦酸 硫酮式异构体 硫醇式异构体 对映异构体 质子转移异构化 

分 类 号：O641.121[理学—物理化学]