【摘要】 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.更多还原

【Abstract】 The transition metal ions incorporation reactions into 5, 10 , 15 , 20-tetrakis (pentafluorophenyl)porphyrin(H2tpfpp) to form the metal porphyrin complexes M(tpfpp) (M= Co, Ni, Zn) have been kineticallyinvestigated using diaquabis(1, 1, 1, 5, 5, 5-hexafluoropentane-2, 4-dionato) metal compounds [M(hfac)2(H2O)2] insupercritical carbon dioxide (scCO2) medium in a spectrophotometric cell. The reactions are first order with respectto H2tpfpp under the conditions where [M(hfac)2(H2O)2] is in large excess relative to H2tpfpp. The saturationdependence of the conditional first-order rate constants as a function of the mole fraction of the excess metalcompounds [M(hfac)2(H2O)2] is observed for the reaction systems [Co(hfac)2(H2O)2+H2tpfpp] and [Ni(hfac)2(H2O)2+H2tpfpp], and the linear dependence is observed for the reaction system [Zn(hfac)2(H2O)2+H2tpfpp]. The mechanismsare discussed and the thermodynamic and kinetic parameters for the reactions are obtained.更多还原