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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)MnIII]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)MnIII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.
Nitrogen-containing ligands such as imidazole, methylimidazole, isopropylimidazole and pyridine were reacted with 5,10,15-tris (pentafluorophenyl) carbazole manganese [(TPFC) MnIII ] And 5,10,15-tris (pentafluorophenyl) carbamanganese [(TPFC) MnVO] have been studied theoretically.The calculated results show that the ligands can react with (TPFC) MnIII form an effective axial coordination, the order of absolute binding energy is: imidazole> 4-methylimidazole> pyridine, consistent with the experimental results.In addition, bond energy and axial coordinate bond length data show that these ligands can not And MnVO in Mn or MnO of ground state (singlet state) or triplet state (TPFC) form an effective axial coordination effect. NBO analysis shows that MnV has no empty 3d orbitals to accept the lone pair electrons , But ligands can form weak coordination with (TPFC) MnVO in triplet state.