(*)NO(2) generated from (*)NO and air add to iron(III) porphyrin upon nitration, which isomerized spontaneously to hydrolysis, yielding a meso-hydroxylated cation that seized by the end oxidation product, a nitrate ion, through extensive hydrogen bonding.

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The iron complexes of 5,10,15-tris(4-nitrophenyl)corrole have been prepared and characterized by various spectroscopic techniques. The (nitrosyl)iron complex is diamagnetic and its X-ray structure reveals an almost perfectly linear Fe–N–O bond. EPR spectroscopy in conjunction with 15N labelling were used to deduce the redox centre of the one-electron reduction and oxidation products of the (nitrosyl)iron corrole.

The synthesis and characterization of manganese complexes of 5,10,15-tris(4-nitrophenyl) corrole in different oxidation states are described. Adoption of established protocols for the synthesis of (nitrido)manganese(V) complexes led to the expected corrole derivative as a minor product, accompanied by nitrogen atom insertion into the macrocycle. The major product was fully characterized via the combination of spectroscopy and X-ray crystallography as (nitrido)manganese(V) 6-azahemiporphycene.

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