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Adding HClO4 to [(BnTPEN)MnIII–OO]+ in MeOH generates a short-lived MnIII–OOH species, which converts to a putative MnV＝O species. The potent MnV＝O species in MeCN oxidizes the pendant phenyl ring of the ligand in an intramolecular fashion. The addition of benzene causes the formation of (BnTPEN)MnIII-phenolate. These findings suggest that high valent Mn species have the potential to catalyze challenging aromatic hydroxylation reactions. [ABSTRACT FROM AUTHOR]

Selective catalytic oxygenation of unactivated C–H bonds for a series of substrates by dioxygen using iron complexes was performed without the use of a co-reductant. Mechanistic studies indicate that the reaction proceeded via the autocatalytic formation of an oxoiron(V) intermediate, which brings high regioselectivity and stereoretention. [ABSTRACT FROM AUTHOR]