The anaerobic reaction of chelated protohaemin, a synthetic model compound of ferrihaemoglobin, with phenyldiazene produced a compound with the visible-absorption spectrum of a ferrihaemochrome. The compound reacted with CN-, which is a ligand of both ferric and ferrous porphyrins, to produce the complex of the synthetic ferrihaemoglobin with CN-. Though the spectrum of the compound formed by the addition of phenyldiazene to chelated protohaemin is characteristic of a ferric porphyrin complex, this compound reacted with both toluene-p-sulphonylmethyl isocyanide and CO, which are strong ligands of ferrous porphyrins, to produce the corresponding ferrous complexes. These ligand-binding reactions indicated that the complex of chelated protohaem with phenyldiazene can behave either as a complex of a ferric porphyrin with phenyldiazenyl anion (C6H5N = N-) or a complex of a ferrous porphyrin with phenyldiazenyl radical (C6H5N = N.). Para substituents on phenyldiazene were without effect on the formation of 4-substituted phenyldiazenyl complexes with chelated protohaem. Ortho substituents resulted in less-stable complexes. The phenyl complex of chelated protohaem was prepared by the aerobic reaction of phenylhydrazine with chelated protohaemin, and its structure was confirmed by its n.m.r. spectrum. The ligand-binding properties, n.m.r. spectrum and absorption spectrum of this complex differed from those of the phenyldiazenyl complex. The phenyl complex also was produced when the phenyldiazenyl complex was exposed to O2.