Acta Phys. -Chim. Sin. ›› 2015, Vol. 31 ›› Issue (6): 1069-1076.doi: 10.3866/PKU.WHXB201504022

• THEORETICAL AND COMPUTATIONAL CHEMISTRY • Previous Articles     Next Articles

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).

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