| 金属离子与卟啉的嵌入反应动力学研究──Ⅶ．一元酸根催化Cu(Ⅱ)与溴化间－四(N－乙酸甲酯基－3－吡啶基)卟啉的配位反应 |
| STUDIES ON KINETICS OF INCORPORATION OF METAL ION INTO PORPHYRIN Ⅶ.REACTION OF Cu￣(2+) WITH TETRAKIS(N-CARBOMETHOXYMETHTHYL-3-PYRIDYL)PORPHYRIN BY THE ANION CATALYSIS OF FATTY ACID |
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| 摘要: 研究了在35±0.1℃、离子强度0.5mol/L(KCl)条件下,甲酸根、乙酸根、丙酸根和丁酸根分别催化Cu(Ⅱ)离子与四溴化间-四(N-乙酸甲酯基-3-吡啶基)卟啉(H2TB-N-ACMSpyPBr4)的反应动力学及其机理,该类反应对卟啉和Cu(Ⅱ)离子均为一级反应,反应动力学方程为:d[Cup4+]/dt=k{(1.0+b[A-])/(1.0+K3.4·[H+]2)}[Cu2+][p]T,在甲酸-甲酸根缓冲体系中,k=2.98mol-1dm3·sec-1,b=154×102mol-2,dm6·sec-1,K3.4=6.928×103;在乙酸-乙酸根缓冲体系中,k=3.42mol-1·dm3·sec-1,b=2.29×103mol-2·dm6·sec-1,K3.4=6.928×103;在丙酸-丙酸根缓冲体系中,k=3.00mol-1·dm3·sec-1,b=5.90×102mol-2·dm6·sec-1,K3.4=7.007×103;在丁酸-丁酸根缓冲体系中,k=3.14mol-1·dm3·sec-1,b=3.75×102mol-2·dm6·sec-1,K3.4=6.921×103;讨论了有机酸根的碱性与催化活性的关系. |
| 关键词: 化学反应动力学 嵌入反应 卟啉 铜离子 |
| 基金项目: 国家自然科学基金 |
| Abstract: Kinctics of the coordination reaction of tctrakis(N-carbomethoxymcthyl0-3-pyridyl)orphyrin with Cu(Ⅱ)ion have been studied in formatc.acetate,propionate and butyrate buffcr solution and in the rangeofpH 3-5 at 35.0±0.1℃ and an ionic strcngth of 0.5mol/ L(KCl).The reaction is found to be first order for both Cu(Ⅱ)and porphyrin and tobe anion catalysis of organic acid.The effcct of concentration of catalyst and metal ion,andpH value of solution were discussed.The rate equation of the rcaction were expressed asd [CuP4+].dt=k{(1.0+b[A-]/1.0+K3.4[H+]2)}[Cu2+][P]T;where k=2.98mol-1·dm+3·scc-1,b=1.54×102mol-2·dm6·sec-1,K3.4=6.928×102,for formate buffer system;k=3.42mol-1·dm·sec-1 b= 229×102mol·dm6·sec-1.K3.4= 5.409 ×103,for acetate system;k=300mol-1·dm3·sec-1,b=5.90×102mol-2·dm·sec-1,K3.4=7.007×103,for propionatesystcm;k=3.14mol-1·dm3·sec-1,b=3.75 ×102mol-2·dm6·scc-1, K3.4= 6.921×103,forbutyrate system.The mechanism of the reaction were proposed.The deformation of the ring ofporphyrins is the general condition in the reaction. |
| Keywords: chemical reaction kinetics incorporate reaction porphyrin copper(Ⅱ) ion |
| 投稿时间：1993-08-07 |
| 摘要点击次数: 1399 |
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| 潘志权,董平安,任建国,秦子斌.金属离子与卟啉的嵌入反应动力学研究──Ⅶ．一元酸根催化Cu(Ⅱ)与溴化间－四(N－乙酸甲酯基－3－吡啶基)卟啉的配位反应[J].无机化学学报,1994,10(3):227-233. |
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