Symmetric intramolecular proton transfers between oxygen atoms in anionic systems. An ab initio study
Symmetric intramolecular proton transfers between oxygen atoms in anionic systems. An ab initio study
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DOI：
10.1021/ja00166a022
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发表时间：
1990-05
影响因子：
15
通讯作者：
E. Bosch;J. M. Lluch;J. Bertrán
中科院分区：
文献类型：
--
作者：
E. Bosch;J. M. Lluch;J. Bertrán
用从头算方法研究了负电荷体系中氧原子的三种对称分子内质子交换。随着反应的进行，电子电荷密度发生了重要的重排。过氧化氢阴离子的0-0键在过渡态断裂，能垒非常大。在水-过氧化氢阴离子络合物中，水分子作为双功能催化剂，0-0键保持形成，能垒显著降低。最后，乙醇酸阴离子中的质子转移通过C^过渡态发生，其总电子电荷密度呈现环状点，能量势垒非常小。
Three symmetric intramolecular proton exchanges involving oxygen atoms in negatively charged systems have been studied by ab initio methods. An important rearrangement of the electronic charge density takes place as the reactions proceed. The 0-0 bond is broken in the hydroperoxide anion at the transition state, the energy barrier being very large. In the water-hydroperoxide anion complex the water moleculeacts as a bifunctional catalyst, the 0-0 bond remaining formed and the energy barrier being significantly lowered. Finally, the proton transfer in the glycolate anion occurs through a C^ transition state whose total electronic charge densitypresents a ring point, the energy barrier being very small.