Réactions des dérivés de l'iode(III) avec les ferroporphyrines et le cytochrome P-450: Formation de complexes σ-aryles du fer(III) et de N-aryl-porphyrines du fer(II) à partir de sels de diaryliodonium

Abstract Diaryliodonium salts ArAr′I + X − , such as diphenyliodonium chloride or iodide ( a and 4b ), p -chlorophenyl(2-thienyl)iodonium chloride ( 5 ) and bis(2-thienyl)iodonium chloride ( 6 ), oxidize Fe II (TPP) (TPP = tetraphenylporphyrin) to give the corresponding ferric porphyrin complex. In the presence of an excess of reducing agent (iron powder), compounds 4 and 5 react with Fe(TPP) to give the σ-aryl complexes, Fe III (TPP)(Ar) (with Ar  C 6 H 5 and p -ClC 6 H 4 , respectively). Using of an excess of 4a or 4b , gave in addition the Fe II (N-C 6 H 5 -TPP)(Cl or I) complexes. Reaction of compounds 4 , 5 and 6 with the hepatic cytochromes P-450 in the presence of NADPH or sodium dithionite, also gave σ-aryl ferric complexes characterized by a Sorek peak around 480 nm.