Synthesis, Spectroscopy, and Novel Reactivity of Metalloporphyrin Compounds

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An extremely important type of chemical reaction is the addition of oxygen atoms to an organic compound, a process called oxidation. The compounds under study in this research project, metalloporphyrins, constitute the active sites of enzymes which carry out biological oxidations and also show great promise as laboratory and industrial catalysts for oxidation reactions. The aims of this project include both the synthesis of new compounds of this type and achieving a more profound understanding of the mechanisms of catalytic action. This project represents in part a continuation of present efforts in the general area of spectroscopic studies of highly oxidized and unusual metalloporphyrin compounds. Newly proposed studies are designed to demonstrate prototype chemical and electrochemical systems for oxidation of hydrocarbon and carbonyl compounds. Preliminary results with iron porphyrin-catalyzed air oxidation of these molecules are particularly noteworthy. Deuterium NMR spectroscopy of the paramagnetic and often highly reactive metalloporphyrin compounds provides a central theme for the five diverse projects described here. Specific objectives include: (1) continued synthetic and reactivity studies of metalloporphyrin complexes with strongly oxidizing oxyanion and thioanion axial ligands; (2) expanded use of fluoroiron complexes for electrocatalytic hydrocarbon oxidations and dioxygen activation; (3) detailed study of chlorine(I) oxide as a metalloporphyrin oxidant, and evaluation of the role of this anhydride in manganese porphyrin mediated hypochlorite oxidation of hydrocarbon compounds; (4) evaluation of various metalloporphyrin derivatives as catalysts for the air oxidation of aldehydes and other cosubstrates; and (5) synthesis of novel metalloporphyrin compounds by insertion of substrates into the iron-carbon bond of alkyl and aryliron porphyrin complexes.