Catalytic reactivity of a meso-N-substituted corrole and evidence for a high-valent iron-oxo species

The single-turnover-like reaction conditions at ?78 degree [Celsius] are used to obtain a new dark-brown species with ([[lambda].sub.max] = 396, 732, 843 nm) from dark-green ([[lambda].max] = 440, 611, 747 nm) complex of iron(III) meso-N-substituted corrole ([TBP.sub.8]Cz)[Fe.sup.III] ([TBP.sub.8]Cz = octakis(4-tert-butylphenyl)corrolazinato). Rapid-mixing stopped-flow UV-vis studies showed that the low-temperature dark-brown complex is generated as a short-lived intermediate at room temperature and EPR spectroscopic characterization established the complex as an antiferromagnetically coupled iron(IV)-oxo [pi]-cation-radical complex.