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通过对Mn(TPP)Cl/NaOCl单加氧酶模拟体系中加入不同轴向配体其电子吸收光谱变化的考察,对影响轴向配体助催化性能的作用因素加以研究,实验表明,具有高位阻效应、较强配位能力的轴向配体表现出优良的助催化性能,轴向配配体本身的pKa数值与其助催化性能并无必然的联系。同时通过对该模型体系催化丙烯环氧化的原位电子吸收谱考察,表明在该催化循环中形成了活性中间络合物:高价的锰氧络合物[Mn(Ⅴ)=O(TPP)Cl]。并根据实验结果提出了该模拟体系催化丙烯环氧化的反应机制。
By investigating the changes of electron absorption spectra of different axial ligands in the simulated system of Mn (TPP) Cl / NaOCl monooxygenase, the factors influencing the cocatalytic performance of axial ligands were investigated. Axial ligands with strong resistance and strong coordination ability show excellent cocatalytic performance. The pKa value of the axial ligand itself is not necessarily related to its cocatalytic performance. At the same time, in-situ electron absorption spectra of propylene epoxidation catalyzed by this model system were investigated. It was found that active intermediate complexes were formed in this catalytic cycle. The high Mn (Ⅴ) = O (TPP) Cl]. Based on the experimental results, the reaction mechanism of the simulation system for the epoxidation of propylene was proposed.