Axial Coordination Behavior of Corrole Mn-III and (MnO)-O-V Complexes with N-Based Ligands

作者：Gong Li Zhen; Xu Zhi Guang^*; Xu Xuan; He Jing; Wang Qi; Liu Hai Yang

来源：Acta Physico - Chimica Sinica, 2014, 30(2): 265-+.

DOI：10.3866/PKU.WHXB201312181

• Corrole
• Manganese
• Manganese-oxo complex
• Density functional theory
• Axial coordination

The axial coordination behavior of the 5,10,15-tris(pentafluorophenyl)corrole manganese [(TPFC)Mn-III] and 5,10,15-tris(pentafluorophenyl) corrole manganese(V)-oxo [(TPFC)(MnO)-O-V] 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-III 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)(MnO)-O-V 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)(MnO)-O-V 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)(MnO)-O-V in its triplet state.

• 出版日期2014-2
• 单位华南理工大学; 华南师范大学