Oxidation of an indole substrate by porphyrin iron(iii) superoxide: relevance to indoleamine and tryptophan 2,3-dioxygenases.

Reaction of FeIII(O2˙-)(TPP) with 2,3-dimethylindole at -40 °C gives the ring-opened, dioxygenated N-(2-acetyl-phenyl)-acetamide product. The reaction was monitored in situ by low-temperature UV-vis and 1H NMR spectroscopies. This work demonstrates that a discrete iron(iii)(superoxo) porphyrin is competent to carry out indole oxidation, as proposed for the tryptophan and indoleamine 2,3-dioxygenases.

The hydrogen atom transfer reactivity of a porphyrinoid cobalt superoxide complex.

The H-atom transfer (HAT) reactivity of a corrolazine cobalt superoxide with weak O-H and N-H substrates has been demonstrated. Kinetic analysis shows relatively fast rates of HAT with diphenylhydrazine (DPH). A kinetic isotope effect (KIE) and Eyring activation parameters are consistent with an HAT mechanism.

Factors Affecting Hydrogen Atom Transfer Reactivity of Metal-Oxo Porphyrinoid Complexes.

There has been considerable interest in hydrogen atom transfer (HAT) reactions mediated by metal/oxygen species because of their central role in metalloenzyme function as well as synthetic catalysts. This Account focuses on our progress in synthesizing high-valent metal-oxo and metal-hydroxo porphyrinoid complexes and determining their reactivities in a range of HAT processes. For these studies we have utilized corrolazine and corrole ligands, which are a ring-contracted subclass of porphyrinoid compounds designed to stabilize high-valent metal complexes.