Characterization of High-Valent Oxo-Metalloporphyrins\rMetal-Oxo and Metal-Peroxo Species in Catalytic Oxidations

Abstract

High-valent oxo metalloporphyrins have been known as reactive intermediates in the catalytic cycles of many heme enzymes and in the oxidation reactions mediated by synthetic metalloporphyrins. In this review, we survey studies of high-valent oxo metalloporphyrins in the past decade. In Sect. 2, electronic structures and magnetic properties of compound I and compound II species in various heme enzymes are discussed on the basis of recent studies of synthetic model complexes of the compound I and compound II. In Sect. 3, spectroscopic properties of oxo manganese porphyrin complexes and their application to biological systems are summarized. In the Sects. 4 and 5, synthesis and characterization of oxo chromium and oxo ruthenium porphyrin complexes are reviewed. In the last section, we have summarized the synthesis and characterization of Mo, Nb, Ti, and V oxo metalloporphyrins complexes.