Acta Phys. -Chim. Sin. ›› 2014, Vol. 30 ›› Issue (2): 265-272.doi: 10.3866/PKU.WHXB201312181

• THEORETICAL AND COMPUTATIONAL CHEMISTRY • Previous Articles     Next Articles

Axial Coordination Behavior of Corrole Mn and MnVO Complexes with N-Based Ligands

GONG Li-Zhen1, XU Zhi-Guang1, XU Xuan1, HE Jing1, WANG Qi2, LIU Hai-Yang2   

  1. 1 Key Laboratory of Theoretical Chemistry of Environment, Ministry of Education, School of Chemistry and Environment, South China Normal University, Guangzhou 510006, P. R. China;
    2 Department of Chemistry, South China University of Technology, Guangzhou 510641, P. R. China
  • Received:2013-10-08 Revised:2013-12-18 Published:2014-01-23
  • 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, 21371059) and Natural Science Foundation of Guangdong Province, China (S2012010008763).

Abstract:

The axial coordination behavior of the 5,10,15-tris(pentafluorophenyl)corrole manganese [(TPFC)Mn] and 5,10,15-tris(pentafluorophenyl)corrole manganese(V)-oxo [(TPFC)MnVO] complexes with N-based ligands, such as imidazole, methylimidazole, isopropylimidazole, and pyridine, were investigated using density functional theory (DFT) at BP86 level. The results show these N-based ligands can form a stable axial coordination complex with (TPFC)Mn in its quintet state. The coordination binding strength followed the order imidazole>4-methylimidazole>pyridine, which is in agreement with experimental results. The binding energy and the large distance between the Mn and N atom of the ligands indicates that (TPFC)MnVO cannot form an effective coordination bond in its singlet or triple state. Natural bond orbital (NBO) analysis indicates that the 3d orbitals of the Mn atom in (TPFC)MnVO are fully occupied, and there are no empty 3d orbitals to accept lone pair electrons from the ligands. However, there is a weak coordination interaction between the ligands and (TPFC)MnVO in its triplet state.

Key words: Corrole, Manganese, Manganese-oxo complex, Density functional theory, Axial coordination

MSC2000: 

  • O641