物理化学学报 >> 2015, Vol. 31 >> Issue (6): 1069-1076.doi: 10.3866/PKU.WHXB201504022

理论与计算化学 上一篇    下一篇

反式双氧锰(V)咔咯配合物的稳定性

章小慧1, 徐志广1, 龚丽珍1, 许旋1, 沈桂贤1, 陈华彬1, 刘海洋2   

  1. 1 华南师范大学化学与环境学院, 教育部环境理论化学重点实验室, 广州510006;
    2 华南理工大学化学系, 广州510641
  • 收稿日期:2015-02-02 修回日期:2015-04-01 发布日期:2015-06-05
  • 通讯作者: 徐志广, 刘海洋 E-mail:chzgxu@scnu.edu.cn;chhyliu@scut.edu.cn
  • 基金资助:

    国家自然科学基金(21171057, 21275057, 21371059)和广东省自然科学基金(S2012010008763)资助项目

Stability of trans-Dioxo Manganese(V) Corrole Complex

ZHANG Xiao-Hui1, XU Zhi-Guang1, GONG Li-Zhen1, XU Xuan1, SHEN Gui-Xian1, CHEN Hua-Bin1, LIU Hai-Yang2   

  1. 1 School of Chemistry and Environment, Key Laboratory of Theoretical Chemistry of Environment, Ministry of Education, South China Normal University, Guangzhou 510006, P. R. China;
    2 Department of Chemistry, South China University of Technology, Guangzhou 510641, P. R. China
  • Received:2015-02-02 Revised:2015-04-01 Published:2015-06-05
  • Contact: XU Zhi-Guang, LIU Hai-Yang E-mail:chzgxu@scnu.edu.cn;chhyliu@scut.edu.cn
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (21171057, 21275057, 21371059) and Natural Science Foundation of Guangdong Province, China (S2012010008763).

摘要:

采用密度泛函理论(DFT)的B3LYP方法对反式双氧锰(V)咔咯配合物阴离子的稳定性及其质子化物种进行了理论计算. 结果表明: 反式双氧锰(V)咔咯配合物阴离子构型稳定, 其反式双氧锰键O=Mn=O由锰原子的d轨道与两个氧原子的p轨道分别构成一个σ轨道和两个π轨道; 随着外围取代基吸电性增强, O=Mn=O键长缩短, 拉曼伸缩振动频率增大; 其质子化过程中得到两个质子的轴向氧原子与锰原子的距离超出正常化学键的范围, 从而形成水分子并脱离原来分子, 导致质子化行为是不可逆过程, 而形成单氧的咔咯锰(V)-氧配合物.

关键词: 密度泛函理论, 反式双氧锰(V)咔咯配合物, 稳定性, 质子化

Abstract:

The stability of anionic trans-dioxo manganese(V) corrole complex and the protonated species structure were investigated using density functional theory (DFT) with B3LYP method. The calculation results show that trans-dioxo manganese(V) corrole complex has one σ and two π orbitals in its O=Mn=O bonds, which are composed of the d orbital of the manganese atom and p orbitals of the two oxygen atoms. Enhancement of the electron-withdrawing ability of substituents results in a decrease in the O=Mn=O bond lengths, and shifts the O=Mn=O Raman stretching vibration to a higher wavenumber. On protonation, one of the axial oxygen atoms gains two protons and is transformed into a water molecule. The manganese atom then cannot hold water tightly to form effective coordination bonds with water. This results in irreversible protonation of the trans-dioxo manganese(V) corrole complex, which leads to formation of an oxomanganese (V) corrole complex.

Key words: Density functional theory, trans-Dioxo manganese(V) corrole complex, Stability, Protonation

MSC2000: 

  • O641