Corrole锰-氧配合物的稳定性研究

对5,10,15-三(五氟苯基)-Corrole(tpfc)Mn(V)≡O配合物的稳定性进行了研究. 以二氯甲烷溶剂为参考，乙醇、正辛醇、乙醚、四氢呋喃、二甲基亚砜、甲苯能加速(tpfc)MnV≡O的衰减，而N’N二甲基甲酰胺、水、乙酸乙酯、丙酮能减缓(tpfc)MnV≡O的衰减. (tpfc)MnV≡O与盐酸、醋酸反应生成(tpfc)MnIV-Cl、(tpfc)MnIV-O2CCH3. (tpfc)MnIII能与咪唑、四甲基咪唑、吡啶形成1:1的配合物，轴向配位常数按Imidazole >4-Methylimidazole >Py顺次减弱，在这些轴向配体存在时，(tpfc)MnV≡O的稳定性显著降低. 轴向配体与(tpfc)MnIII的结合导致其MnIII/MnIV半波电位降低. XPS实验结果显示(tpfc)MnIII与轴向配体结合后，其中心金属锰的结合能Mn2p3/2减少，减少程度与轴向配体的给电子能力有关.

Stability of Manganese-Oxo Corrole

The stability of 5,10,15-tris(pentafluorophenyl)Corrole (tpfc) manganese(V)-Oxo corrole in different solvents and in the presence of axial ligand were investigated. The results show ethanol, octanol, ethyl ether, tetrahydrofuran, dimethyl sulfoxide and toluene can accelerate (tpfc) MnV≡O decay by using dichloromethane as reference, and N'N-dimethyl formamide, water, ethyl acetate, acetone can slow down (tpfc)MnV≡O decay. (tpfc)MnIV-Cl, (tpfc)MnIV-O2CCH3 were produced by the reaction of (tpfc)MnV≡O and hydrochloric acid and acetic acid. The axial coordination of (tpfc) MnIII by imidazole, 4-methylimidazole, pyridine give complexes with molar ratio of 1:1. The association constants follow an order of Imidazole >4-Methylimidazole >Py. In the presence of these axial ligands, the stability of (tpfc)MnV≡ O decreased significantly. The MnIII/MnIV half-wave potential of (tpfc) MnIII moved negatively upon combination with axial ligand. XPS results showed that the binding energy of center manganese Mn2p3/2 decreased after axial coordination by the ligand, and the reduction degree depends on the electron-donor capacity of axial ligand.