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用紫外-可见光谱研究了钴(II)、镍(II)、锌(II)的1,1,1,5,5,5-六氟-2,4-戊二酮-二水配合物[M(hfac)2(H2O)2,M=Co、Ni、Zn]与5,10,15,20-四(五氟苯基)卟啉[H2tpfpp]在超临界二氧化碳中反应生成金属卟啉[M(tpfpp)]的反应动力学.在金属配合物大大过量时,反应对卟啉为一级.其表观一级速率常数随钴(II)、镍(II)配合物的浓度增加先增加、而后趋于稳定,而表观一级速率常数随锌(II)配合物的浓度增加线形增加.根据实验事实,讨论了反应的机理,得到了相应的热力学和动力学参数.
The 1,1,1,5,5,5-hexafluoro-2,4-pentanedione-dihydrate complex of cobalt (II), nickel (II) and zinc (II) has been studied by UV- M (hfac) 2 (H2O) 2, M = Co, Ni, Zn] reacted with 5,10,15,20-tetrakis (pentafluorophenyl) porphyrin [H2tpfpp] in supercritical carbon dioxide to form metalloporphyrins [ M (tpfpp)] reaction kinetics.When the metal complex is in a large excess, the reaction of porphyrin is first order.The apparent first order rate constant increases first with the increase of cobalt (II) and nickel (II) complexes , And then tends to be stable, whereas the apparent first-order rate constant increases linearly with the concentration of zinc (II) complex.According to experimental facts, the reaction mechanism is discussed and the corresponding thermodynamic and kinetic parameters are obtained.