The interaction of aniline with hemin during O2 activation and insertion mediated by the metalloporphyrin was studied by a combined theoretical, semiempirical and experimental approach. Association is via a planar .pi. bonding interaction between the aromatic .pi. electrons of the amine and tetrapyrrole ring system. The effect of very high concentrations of hydroxyl radical scavengers on the system is discussed. [This is a model system for cytochrome P-450.].