采用密度泛函理论(DFT)的BP86方法对含氮配体咪唑、甲基咪唑、异丙基咪唑和吡啶与5,10,15-三(五氟苯基)咔咯锰[(TPFC)MnI I]和5,10,15-三(五氟苯基)咔咯锰氧[(TPFC)MnVO]的轴向配位性质进行理论研究。计算结果表明配体能与五重态下的(TPFC)MnI I形成有效的轴向配位作用,结合能绝对值次序为：咪唑>4-甲基咪唑>吡啶,与实验结果一致。另外,结合能和轴向配位键长数据显示,这些配体不能与基态(单重态)或三重态(TPFC)MnVO中的MnV原子形成有效的轴向配位作用,自然键轨道(NBO)分析表明其MnV没有空的3d轨道来接受配体的孤对电子,但配体可与三重态下的(TPFC)MnVO形成弱的配位作用。%The axial coordination behavior of the 5,10,15-tris(pentafluorophenyl)corrole manganese [(TPFC)MnI I] 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)MnI I 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 ful y 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.
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