Abstract − Analytical Sciences, 20(2), 369 (2004).
Interfacial Hydrolysis in the µ-oxo Dimer Formation of Tetraphenylporphinatomanganese(III) in the Toluene/Water System
Kazuhiko FUJIWARA and Hitoshi WATARAI
Department of Chemistry, Graduate School of Science, Osaka University, Toyanaka, Osaka 560-0043, Japan
The interfacial adsorption and dimerization behavior of tetraphenylporphinatomanganese(III)chroride (Mn(TPP)Cl) in the toluene/water two phase system was studied. The absorption spectra of the porphyrin complex in the organic phase were blue shifted with increasing of pH in the aqueous phase, suggesting the formation of the µ-oxo dimer. The interfacial species in these systems were examined by means of UV/vis external reflection (ER) spectrophotometry. ER spectral maxima were also blue shifted with the increase in pH, whereas the shape of the ER spectra in the basic conditions was different from that of the µ-oxo dimer. The observed results suggest that the hydroxide-coordinated monomer, Mn(TPP)OH, was generated from the Mn(TPP)(H2O)+ at the interface under the basic conditions and that was further converted to the µ-oxo dimer, which was soluble into the toluene phase.
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