A Bulky Bis-Pocket Manganese(V)-Oxo Corrole Complex: Observation of Oxygen Atom Transfer between Triply Bonded Mn~v=O and Alkene

摘要

Reactive Mn-oxo species have been implicated as intermediates in the oxidation of water to oxygen in Photosystem II as well as in certain catalases and oxygen atom transfer (OAT) reactions. While Mn-catalyzed oxidations of organic substrates involving numerous Mn~Ⅲ-oxo, Mn~Ⅳ-oxo, and Mn~Ⅴ-oxo,complexes have been extensively studied, the factors controlling the reactivity of Mn-oxo complexes are not completely understood, and the current literature on Mn-oxo chemistry is not without controversy. An example is Mn~Ⅴ-oxo porphyrin, which is one of the most studied Mn~Ⅴ-oxo systems but exhibits a wide range of reactivity in OAT reactions. Recently, a definitive characterization of the inert trans-dioxo Mn(Ⅴ) porphyrins has greatly enhanced our understanding of the structure and properties of Mn-oxo complexes.