| 属离子与卟啉的嵌入反应动力学研究(Ⅷ)meso-四对羟基苯卟啉与铜(Ⅱ)在DMF中的配位反应 |
| Kinetics Study on the Incorporating Metal Ion into Porphyrin Ⅷ —Formation reaction of CuⅡ and meso-tetra-p-hydroxylphenyl porphyrin compound in Dimethylfermamide |
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| 摘要: 在35.0±0.1℃、离子强度0.1(0.1mol·L-1NaClO4)条件下,研究了在N,N'-二甲基甲酰胺溶液中meso-四对羟基苯卟啉与CuⅡ的配位反应动力学。根据在此体系中CuCl2的缔合状态,溶液氢离子浓度对反应速率的影响,得到铜Ⅱ卟啉生成反应的动力学方程,测量了该反应的活化参量。结果表明反应遵循缔合离解机理,活性中间体的离解是反应的决速步骤。 |
| 关键词: meso-四对羟基苯卟啉 嵌入反应动力学 铜卟啉的生成反应 |
| 基金项目: 国家自然科学基金(No.29871024);湖北省自然科学基金 |
| Abstract: Kinetics of the coordination reaction of meso-tetra-p-hydroxylphenyl porphyrin(abbr. TP OHTPP) with CuⅡ in dimethylformamide(DMF) has been studied under 35.0±0.1℃ and with ion strengh 0.1(NaClO4). The kinetic equation of the formation reaction of the metalloporphyrin has been obtained as d[CuⅡP]/dt = k [CuCl+][P]T/(1.0+[H+]/Ka3+[H+] 2/ Ka3 Ka4), k =0.4671 L2·mol-2·s-1, Ka3 =2.226×10-3, Ka4 = 3.691×10-4, accorting to the associated states of CuCl2 in DMF and the dependence of reaction rate on both [CuⅡCl+] and [H+]. The active parameters of the reaction have been investigated as Ea = 81.86 kJ·mol-1·K-1, ΔH ≠= 80.39 kJ·mol-1, ΔG≠= 64.20 kJ·mol-1 and ΔS≠= 52.55J·mol-1·K-1. The results of the study shows that the reaction follows the mechanism of association dissociation with its rate limit step of the dissociation of the activeted complex[CuCl+…H2P]. |
| Keywords: meso-tetra-p-hydroxylphenyl porphyrin kinetics of incorporation reaction formation reaction of copperⅡ porphyrin |
| 投稿时间：1999-10-15 |
| 摘要点击次数: 1105 |
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| 魏祖期,王运宏,任建国,秦子斌.属离子与卟啉的嵌入反应动力学研究(Ⅷ)meso-四对羟基苯卟啉与铜(Ⅱ)在DMF中的配位反应[J].无机化学学报,2000,16(2):329-334. |
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