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本文报道了在硝酸汞催化下Mn(Ⅱ)与四溴化四(N-乙酸甲酯基-3-吡啶基)卟啉在硼砂缓冲溶液中的反应动力学和机理。实验表明,Hg(Ⅱ)催化Mn(Ⅱ)对该类卟啉的嵌入反应是通过“坐式(SAT)”中间配合物(Hg-SAP)而完成的;在讨论催化剂浓度、溶液的pH值对反应影响的基础上,得到了表观速率常数表达式κ_(obs)=[Hg~(2+)][Mn~(2+)]/(κ_o[H~+]+k[Mn~(2+)]),其中κ_o=26.20mol·dm~(-3)·s,κ=2.59×10~(-5)mol·dm~(-3)·s,提出了该反应的机理和模式,进而论证了卟啉环的变形是金属离子通过“SAT”中间化合物嵌入卟啉反应的必要条件。
The reaction kinetics and mechanism of Mn (Ⅱ) with tetrakis (N-methyl-3-pyridyl) tetrabromide in borax buffer solution catalyzed by mercury nitrate were reported. The experimental results show that the Hg (Ⅱ) -catalyzed Mn (Ⅱ) intercalation reaction with these porphyrins is accomplished through the “sit-in” (SAT) intermediate complex (Hg-SAP) On the basis of the influence on the reaction, the apparent rate constant expression κ obs = [Hg ~ (2 +)] [Mn ~ (2 +)] / (κ_o [H ~ +] + k [Mn ~ 2+)], where κo = 26.20mol · dm -3 · s and κ = 2.59 × 10 -5mol · dm -3 · s, the mechanism and mode of the reaction are proposed , And then proves that the deformation of the porphyrin ring is a necessary condition for metal ions to be embedded in the porphyrin reaction through the “SAT” intermediate compound.