甲氧基硫代膦酰二氯自身异构化反应机理的理论研究

Theoretical Study on the Self-isomerization Reaction Mechanism of Methoxy-thiophosphoryl Dichloride

用量子化学从头计算方法在HF/ 6 3 1G水平上研究了甲氧基硫代膦酰二氯自身异构化反应的微观机理 ,优化得到了反应物、过渡态和产物的几何构型 ,经振动分析确证了过渡态的真实性 .研究结果表明该异构化反应先形成一个四元环过渡态而后转变为产物 .反应活化能为 14 .3kJ/mol,反应放热 12 0 .6kJ/mol,是一个易于进行的异构化反应 .

The self isomerization reaction mechanism of methoxy thiophosphoryl dichloride is studied by ab initio at the level of theory HF/6 31 G . The geometries of the reactant, the product and the transition state have been calculated. The calculation of frequency has proved existence of the transition state. The obtained results show the isomerization reaction first forms a four membered ring transition state and then the product is got. The activation energy of the reaction is 14.3 kJ/mol and the reaction heat is 120.6 kJ/mol, so the isomerization reaction is easily obtained.