The synthesis, characterisation and homogeneous catalytic oxidation results of two manganese(III) porphyrins of the so-called second-generation of metalloporphyrin catalysts, containing one or four 3,5-dichloropyridyl substituents at the meso positions are reported for the first time. The catalytic efficiency of these novel manganese(III) porphyrins was evaluated in the oxidation of cyclooctene and styrene using aqueous hydrogen peroxide as the oxidant, under homogeneous conditions. High conversions were obtained in the presence of both catalysts, obtaining the corresponding epoxide as the major product. The asymmetric metalloporphyrin, chloro[5,10,15-tris(2,6-dichlorophenyl)-20-(3,5-dichloropyridin-4-yl)porphyrinate]manganese(III), CAT-4, evidences a similar activity to that obtained with the well-known and highly efficient second-generation metalloporphyrin catalyst, chloro[5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrinate]manganese(III), CAT-2. CAT-4 was covalently attached onto Merrifield resin and 3-bromopropylsilica supports. The solid materials obtained were characterized by several techniques including diffuse reflectance, UV—VIS spectrophotometry, SEM and XPS. The catalytic results for the oxidation of cyclooctene and styrene using the immobilized catalysts are also presented. The Merrifield-supported catalyst showed to be very efficient, leading to five catalytic cycles in the oxidation of cyclooctene, using tert-butyl hydroperoxide as the oxidant.
A Combined Computational and Experimental Study of Methane Activation during Oxidative Coupling of Methane (OCM) by Surface Metal Oxide Catalysts
