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在不同离子强度的高氯酸钠水溶液中,用分光光度法测量自由卟啉H_2T_(β-N-EAES)PyPBr_4(简记为H_2P~(4+))与Gu(Ⅱ)离子的配位反应动力学,探讨高氯酸钠对Cu(Ⅱ)离子嵌入自由卟啉反应的催化本质.在给定条件下,高氯酸根与自由卟啉的缔合数n为1;缔合平衡常数K_0=3.70±0.42dm~3.mol~(-1).配位反应实验动力学方程为d[Cu(Ⅱ)P~(4+)]/dt=5.55×10~5γCu~2+γH_2P~4+γ(3)[ClO_4~-]~3[Cu~(2+)][H_2P]_总/(1.00+10~(2.02{H+}+10~(4.36{H~+}~2)、反应的活化能E=53.30kJ·mol~(-1),活化焓变△H~ =50.31kJ·mol~(-1),活化熵变△S~ =-77.65J·mol~(-1)·K~(-1).提出了金属卟啉生成反应中的ClO_4~-催化卟啉环变形的反应机理.
The coordination reaction of PyPBr_4 (abbreviated as H_2P ~ (4+)) and Gu (Ⅱ) ion of free porphyrin H_2T_ (β-N-EAES) was measured by spectrophotometry in aqueous solution of sodium perchlorate with different ionic strength Kinetics to explore the catalytic nature of sodium perchlorate on Cu (Ⅱ) intercalation into the free porphyrin reaction.Under the given conditions, the association number of perchlorate with free porphyrin is 1 and the association constant K_0 = 3.70 ± 0.42dm ~ 3.mol ~ (-1). The kinetic equation of coordination reaction is d [Cu (Ⅱ) P ~ (4 +)] / dt = 5.55 × 10 ~ 5γCu ~ 2 + γH_2P ~ 4 + γ (3) [ClO_4 ~] ~ 3 [Cu ~ (2 +)] [H_2P] _Total /(1.00+10~(2.02{H+}+10~(4.36{H~+}~2)), reaction The activation energy E = 53.30kJ · mol -1, the activation enthalpy △ H ~ = 50.31kJ · mol -1, the activation entropy change △ S ~ = -77.65J · mol -1 · K ~ (-1). The reaction mechanism of ClO_4 ~ - catalyzed porphyrin ring deformation in metalloporphyrin production was proposed.