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Citation: LIU Shi-jun, CHEN Qi-yuan, FUNAHASHI Shigenobu. Kinetic Study of the Reactions of Porphyrin with Co(II), Ni(II) and Zn(II) Compounds in Supercritical Carbon Dioxide[J]. Acta Physico-Chimica Sinica, ;2005, 21(08): 893-897. doi: 10.3866/PKU.WHXB20050814 shu

Kinetic Study of the Reactions of Porphyrin with Co(II), Ni(II) and Zn(II) Compounds in Supercritical Carbon Dioxide

1.
College of Chemistry and Chemical Engineering, Central South University, Changsha 410083； Department of Chemistry, Na ya University, Na ya 464-8602, Japan

Received Date: 27 December 2004
Available Online: 15 August 2005

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 kinetically investigated using diaquabis(1, 1, 1, 5, 5, 5-hexafluoropentane-2, 4-dionato) metal compounds [M(hfac)2(H2O)2] in supercritical carbon dioxide (scCO2) medium in a spectrophotometric cell. The reactions are first order with respect to H2tpfpp under the conditions where [M(hfac)2(H₂O)₂] is in large excess relative to H2tpfpp. The saturation dependence of the conditional first-order rate constants as a function of the mole fraction of the excess metal compounds [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 mechanisms are discussed and the thermodynamic and kinetic parameters for the reactions are obtained.
- Transition metal;Porphyrin;Supercritical CO₂;Kinetics
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