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采用密度泛函理论B3LYP方法计算了一种非血红素四氮杂轮烯配合物[Fe(Ⅲ)TMTAA]催化H2O2歧化的反应机理.对二重态、四重态和六重态势能面上各驻点进行了全优化,发现反应易于沿四重态势能面发生.整个反应分两阶段进行,第一阶段通过氧氧均裂形成中间体IM6和第一个水,第二阶段经两次氢转移形成第二个水.反应决速步骤为O—O均裂步骤,能垒为63.9kJ·mol-1,相对于自由H2O2均裂所需能垒226.7kJ·mol-1有较大的降低.这表明标题配合物可有效地降低标题反应的能垒,有可能作为一种潜在的过氧化氢仿酶.
The reaction mechanism of disproportionation of H2O2 catalyzed by [Fe (Ⅲ) TMTAA], a nonheteretetraazepurrene complex, was calculated using the density functional theory B3LYP method. For the doublet, quadruplet and The site was fully optimized and the reaction was found to occur easily along the potential field of the quadruple state.The whole reaction proceeded in two stages: the first stage was formed by the cleavage of oxygen and oxygen to form the intermediate IM6 and the first water, and the second stage was hydrogenated twice The formation of the second water reaction step for the O-O uniform cracking step, the energy barrier is 63.9kJ · mol-1, compared with the free energy barrier H2O2 226.7kJ · mol-1 have a greater reduction. This shows that the title complex can effectively reduce the energy barrier of the title reaction, possibly as a potential hydrogen peroxide-like enzyme.