title: Interfacial hydrolysis in the mu-oxo dimer formation of tetraphenylporphinatomanganese(III) in the toluene/water system.
abstract: 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 mu-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 mu-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 mu-oxo dimer, which was soluble into the toluene phase.
authors.affiliation: Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan.
authors.forename: Kazuhiko
authors.initials: K
authors.lastname: Fujiwara
authors.forename: Hitoshi
authors.initials: H
authors.lastname: Watarai