ION RADICALS .45. REACTIONS OF ZINC TETRAPHENYLPORPHYRIN CATION RADICAL PERCHLORATE WITH NUCLEOPHILES

Details are given of the reactions of zinc tetraphenylporphyrin cation radical perchlorate (ZnTPP+., ClO4-)with pyridine, triphenylphosphine, triphenylarsine, nitrite ion, thiocyanate ion, methanol, water, ammonia, methylamine, and dimethylamine. Reaction with the first five of these nuclophiles gave ZnTPP and a β-substituted ZnTPP according to the usual stoichiometry of reactions of aromatic cation radicals with nucleophilies. From the reaction with nitrite ion a bilitriene was also obtained, identical with that reported earlier by Evans and Smith. The bilitriene was also obtained from reaction with water in tetrahydrofuran. Reaction with methanol gave a meso-substituted methoxyisoporphyrin, previously isolated by Dolphin et al. from reaction of ZnTPP2+with methanol. Reaction with ammonia and the amines gave large yields of ZnTPP. The way in which the bilitriene is formed, the problem of electron exchange with nitrite ion, and the reaction with methanol are discussed. © 1979, American Chemical Society. All rights reserved.