The kinetics and mechanism of aerobic photooxidation of sulfides in the presence of a series of electron-rich and electron-deficient porphyrins immobilized on Amberlyst 15 nanoparticles in the form of porphyrin diacids are reported.
High valent Mn(O) species of a series of electron-rich and -deficient meso-tetra(aryl)porphyrins (aryl = phenyl, 2-Cl-phenyl, 2-nitrophenyl, 2-Me-phenyl, 2-Br-phenyl, 2,6-di-Cl-phenyl 4-OMe-phenyl, 4-Me-phenyl, 4-Cl-phenyl and 4-pyridyl) were prepared at 273 K.
A study of the kinetics and mechanism of the oxidation of a series of electron-rich and electron-deficient benzyl alcohols and cyclohexanol with high-valent manganese oxo species formed by the reaction of meso-tetrakis (2,6-dichlorophenyl)porphyrinatomanganese(III) acetate [Mn(TDClPP)(OAc)] and tetra-n-butylammonium oxone (TBAO) in the presence of imidazole (ImH) are reported. The use of Mn(TDClPP)(OAc), ImH, and TBAO in a 1:15:1000 molar ratio led to the exclusive formation of [(ImH)Mn V (O)(TDClPP)] + (λ max = 408 nm), whereas a mixture of [(ImH)Mn V (O)(TDClPP)] + , (ImH)Mn IV (O)(TDClPP) (λ max = 421 nm), and (ImH)(peroxymonopersulfate)-Mn III (TDClPP) (λ max = 473 nm) was observed for molar ratios lower than this. The formation of [(ImH)Mn V (O)(TDClPP)] + and (ImH)Mn IV (O)(TDClPP) from the catalyst precursor was evidenced in the UV/Vis absorption spectrum of the intermediates at 273 K in dichloromethane. Owing to the different reactivities [a]
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