Study of Synthesis of #mu#-Oxo-bismanganese (III)Porphyrin Compounds and Their Catalysis of Cyclohexane Oxidation by PhlO

摘要

Ten substituted #mu#-oxo-bis[tetraphenylporphinatomanganese (III)] compounds ([TPPMn~(III)]_2O) were synthesized by the reaction of chloro[tetraphenylporphinatomanganese(III)] (TPPMn~(III)Cl) with NaOH. Their catalysis of cyclohexane monooxygenation by PhIO under moderate conditions was studied. In contrast with other metalloporphyrins reported so far, #mu#-oxo-bis[tetraphenylporphinatomanganese(III)] compounds are shown to have better catalytic power for cyclohexane hydroxylation by PhIO. The kinetic research showed that the rate constants k of the cyclohexane reactions had a Hammett relationship to the characteristic constants #sigma# of substitutents R on prophyrin rings.