Kinetics of Incorporation of Zinc (II) into Tetraphenylporphine in N, N-Dimethylformamide. I. Monohydroxo and Acetato Complexes

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The kinetics of incorporation of zinc (II) into meso-tetraphenylporphine in N, N-dimethylformamide (DMF), at 30°, were affected by the trace water in the solvent and by the presence of acetate ion (OAc-). The reaction was one half order in Zn (ClO_4)_2・6H_2O, whereas first order in Zn (ClO_4)_2・6DMF. Addition of HClO_4 to the water containing system retarded the reaction rate and converted the kinetics to the first order with respect to total Zn (II). The main path for the reaction of Zn (ClO_4)_2・6H_2O was concluded to be that involving the monohydroxo species, Zn (OH)^+. Addition of acetate anion increased the rate, until at a ratio [OAc-]/[Zn] of unity the rate reached a maximum ; an increase of the ratio past unity caused a rate decrease. The species, Zn (OAc)^+, is concluded to be more reactive than the fully solvated Zn (II) species and Zn (OAc)_2・
公益社団法人日本薬学会の論文
1978-04-25