| 氢氧化2，9，16，23-四羧基酞菁合铁(Ⅲ)与硫醇轴配反应 |
| AXIAL COORDINATION REACTIONS OF 2,9,16,23-TETRACARBOXYPHTHALOCYNINEIRON(Ⅲ) HYDROXIDE WITH THIOLS |
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| 摘要: 用分光光度法研究了酞菁合铁［Fe(Ⅲ)Pc(COOH)4OH-］与β-羟基乙硫醇(HOCH2CH2SH)的轴向配位反应热力学，求得了配位数(n)，稳定常数(βn)及热力学参数ΔrH0m、ΔrS0m。用停流法研究了［Fe(Ⅲ)Pc(COOH)4OH-］与β-羟基乙硫醇及苯硫酚的轴配反应动力学，讨论了反应机理，求得了预平衡步的平衡常数(K)和速控步的速率常数(k)；研究了温度等诸因素对反应动力学的影响，得到了预平衡的ΔrH0m、ΔrS0m和速控步的活化参数Δ≠Hm、Δ≠Sm |
| 关键词: 氢氧化2，9，16，23-四羧基酞菁合铁(Ⅲ) 硫醇 轴配反应热力学及动力学 停流法 分光光度法 |
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| Abstract: The thermodynamic and kinetic properties were studied for the axial coordination reaction (1) of 2,9,16,23-tetracarboxyphthalocynineiron(Ⅲ) with thiols in potassium hydroxide solution ［Fe(Ⅲ)Pc(COO-)4OH-］+RS-=［Fe(Ⅲ)Pc(COO-)4(RS-)］4-+OH-(1) The equilibrium constant (βn) and coordination number of reaction (1) were measured by spectrophotometry. The standard molar enthalpy (ΔrH0m) and standard molar entropy (ΔrS0m) of the reaction (1) were calculated. Kinetics of the reaction (1) was studied by means of stopped-flow method. The reasonable mechenism of the reaction was postulated, and the pre-equilibrium constant and rate constant were obtained. The standard molar enthalpy and standard molar entropy of the pre-equilibrium step and the activation parameters of the rate controling step were calculated. |
| Keywords: 2,9,16,23-tetracarboxyphthalocynineiron(Ⅲ) hydroxide thiols thermodynamics and kinetics of axial coordinational reaction stopped-flow method spectrophotometer |
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| 周毅,张智慧,朱志昂,冯海霞,阮文娟,陈荣悌.氢氧化2，9，16，23-四羧基酞菁合铁(Ⅲ)与硫醇轴配反应[J].无机化学学报,1998,14(4):388-392. |
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