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Photochemical Generation And Kinetic Studies Of High-Valent Metal-Oxo Intermediates Supported By Corrole And Porphyrin Ligands, Ngo Fung Lee
Photochemical Generation And Kinetic Studies Of High-Valent Metal-Oxo Intermediates Supported By Corrole And Porphyrin Ligands, Ngo Fung Lee
Masters Theses & Specialist Projects
High-valent transition metal-oxo intermediates are of fundamental importance because of their central role as active oxidizing species in enzymatic and synthetic catalytic oxidations. Many transition metal catalysts have been extensively studied as models of the ubiquitous cytochrome P450 enzymes to probe the sophisticated oxygen atom transfer mechanism as well as to invent enzyme-like oxidation catalysts.
In this work, photolysis of highly photo-labile corrole-manganese(IV) bromates or nitrites by visible light was studied in two corrole systems with different electronic environments. The corrole systems under studied include 5,10,15- tris(pentafluorophenyl)corrole (TPFC) and 5,10,15-triphenylcorrole (TPC). As observed in both systems, homolytic cleavage of O-Br …
Synthetic Investigation On The Biomimetic Metal-Catalyzed Sulfoxidations And Photochemical Generation Of A Highly Reactive Ruthenium(V)-Oxo Porphyrin, Weilong Luo
Masters Theses & Specialist Projects
Catalytic oxidation plays a crucial role in current chemical and pharmaceutical industries which is also a leading technology for green chemical processes. In Nature, the ubiquitous cytochrome P450 enzymes can catalyze a wide variety of oxidation reactions with high efficiency and selectivity. Many transition metal catalysts are designed as the biomimetic model of cytochrome P450 enzymes. In this work, series of metalloporphyrins and metallocorroles have been successfully synthesized to investigate and develop catalytic selective oxidation of sulfides to sulfoxides.
Manganese(III) porphyrin complexes (2) and manganese(III) corrole complexes (6) with iodobenzene diacetate [PhI(OAc)2] as a mild oxygen source exhibited remarkable catalytic …