Oxygen oxidation of ethylbenzene over manganese porphyrin is promoted by the axial nitrogen coordination in powdered chitosan

Abstract

A less wasteful production method of oxidation ethylbenzene to acetophenone and phenethyl alcohol was adviced. It revealed an important role in tuning catalytic reactivity of metalloporphyrins by the axial ligand for oxidation of hydrocarbon.

Mesoporous chitosan‐immobilized iron tetrakis(4‐carboxyphenyl)porphyrin as a model of cytochrome P‐450 enzyme for oxidation of ethylbenzene

“…The acylation and coordination of Fe TCPP on mesp‐CTS(or macp‐CTS) changed electron cloud density of all elements, especially the Fe and elements(Cl, N) around it in Fe TCPP. These changes were seen and assigned in Figure and in Table . When the amino groups of mesp‐CTS were acylated by Fe TCPP, and the coordination of amino groups in mesp‐CTS to Fe TCPP occured, these reactions could cause the following Binding Energy(BE) changes: First, the BEs of nitrogen element in the NH 1 or 2 –C sp 3 unit of CTS increased about 1.6 eV.…”

Highly Active Catalysis of Cobalt Tetrakis(pentafluorophenyl)porphyrin Promoted by Chitosan for Cyclohexane Oxidation in Response‐Surface‐Methodology‐Optimized Reaction Conditions

“…This natural structure makes the enzyme, its related artificial enzyme and biomimetic catalyst having excellent functionality and becoming an important catalyst used for substrate oxidation . Duplication of the core structure and part functions of the enzyme using immobilized metalloporphyrin systems is of tremendous interest in order to improve the performance (activity and reusability) of metalloporphyrins . The effect of N‐bases axial coordination on the catalytic activity of metalloporphyrin has been studied about 20–30 years ago, and some achievements were obtained ,.…”

“…For further avoiding use of any solvents and reductants (toxic or not), some studies have been efficiently made on hydrocarbon oxidation at relatively high temperature catalyzed by metalloporphyrin and supported ones ,,. Based on the consideration of practical application in green chemical industry, the improved Lyon system was preferred for us ,,…”

“…[1][2][3][4] Duplication of the core structure and part functions of the enzyme using immobilized metalloporphyrin systems is of tremendous interest in order to improve the performance (activity and reusability) of metalloporphyrins. [3][4][5][6][7][8][9][10] The effect of N-bases axial coordination on the catalytic activity of metalloporphyrin has been studied about 20-30 years ago, and some achievements were obtained. [3,[11][12][13] At present, some new studies on the effect of the axial ligand on catalytic activity of metalloporphyrins [3,8,9] suggested that, the enhanced catalytic activity was attributed to the increased electron donation ability and favoring the formation of the ferryl-oxo species, and that the "push" effect prevails over the "pull" effect.…”

“…[20,27,28] Based on the consideration of practical application in green chemical industry, the improved Lyon system was preferred for us. [10,17,18] We aimed at elevating catalytic performances (activity and reusability) of cobalt tetrakis(pentafluorophenyl)porphyrin (Co TPFPP), and report in here that, cobalt tetrakis(pentafluorophenyl)porphyrin was covalently and coordinately bound to np-and nonp-CTS, forming new catalysts, Co TPFPP/np-or nonp-CTS. Both catalysts were used for cyclohexane oxidation under optimized reaction conditions via a response surface methodology (RSM).…”