Biomimetic oxidation of organosulfur compounds with hydrogen peroxide catalyzed by manganese porphyrins
A biomimetic and environmentally benign approach, with potential application in the oxidative desulfurization procedure for several organosulfur compounds (thioanisol, diphenylsulfide, benzothiophene, 2-methylbenzothiophene, 3-methylbenzothiophene, benzothiophene-2-methanol and dibenzothiophene), is presented. The current methodology involves manganese porphyrins as catalysts, which are well-known biomimetic models of cytochrome P450 enzymes, and hydrogen peroxide as the oxygen source. [Mn(TDCPP)Cl] and [Mn(TPFPP)Cl], the manganese porphyrin complexes used in this study, proved to be very efficient catalysts, affording high conversions of all the substrates tested into the corresponding sulfones. The conversion of benzothiophene reaches 99.9% in 90 min, whereas the conversion of dibenzothiophene attains 99.9% after 120 min of reaction, both for a catalyst/substrate molar ratio of 150. The substituted benzothiophenes give rise to similar results, being the best conversions obtained for a catalyst/substrate molar ratio of 150. The oxidation of a model fuel (solution of benzothiophene, 3-methylbenzothiophene, 2-methylbenzothiophene, and dibenzothiophene in hexane) was performed using hydrogen peroxide and [Mn(TDCPP)Cl] as catalyst, achieving total conversion into the corresponding sulfones.
Graphical abstractFigure optionsDownload full-size imageDownload high-quality image (60 K)Download as PowerPoint slideHighlights► Manganese porphyrins as catalysts and hydrogen peroxide as the oxygen source. ► A biomimetic approach for the oxidation of organosulfur compounds. ► Conversion of benzothiophene reaches 99.9% in 90 min of reaction. ► Conversion of dibenzothiophene attains 99.9% after 120 min of reaction. ► Total conversion of a model fuel in hexane into the corresponding sulfones after 180 min.
Journal: Applied Catalysis A: General - Volumes 439–440, 10 October 2012, Pages 51–56