Diiron complexes on macrocyclic porphyrin-like platform as oxidation catalysts: reactivity and mechanistic considerations

Abstract

Diiron macrocyclic complexes have been often considered as catalytically inert. However, numerous published examples of the catalytic oxidation reactions mediated by these complexes indicate their potential in catalysis. Mechanistic background for their applications as oxidation catalysts and their relationship with enzymatic and biomimetic oxidation involving cytochrome P-450 and soluble methane monooxygenase are discussed. A special emphasis was put on the N-bridged diiron phthalocyanine complexes as an emerging class of oxidation catalysts. Their unusual Fe(μN)Fe structure has interesting catalytic properties and reactivity. In addition to oxidation of strong C–H bonds in alkanes including methane, aromatic, and alkylaromatic compounds, μ-nitrido diiron phthalocyanines catalyze the oxidative dehalogenation and the formation of C–C bonds. A clean and practical character of the catalytic systems coupled with real availability of the phthalocyanines suggests a possibility of the application of this approach in industry. Great potential for further developments by modification of the catalysts structure can be envisioned.