Vicarious nucleophilic substitution of hydrogen and synthesis of nickel-, copper-, and cobalt-porphyrinates– double functionalized at the β-positions of the same pyrrole unit

2-Nitro-5,10,15,20-tetraphenylporphyrin–nickel(II), –copper(II), and –cobalt(II) complexes reacted with carbanions of halomethyl aryl sulphones and para-chlorophenoxyacetonitrile according to the vicarious nucleophilic substitution scheme. This leads to the substitution of hydrogen products, in the position ortho- to the NO 2 group, thus giving β,β-disubstituted derivatives on the same pyrrole ring. The yields were satisfactory, up to 95%. These types of products, being practically unavailable by alternative methods, are attractive starting materials for the synthesis of more complex porphyrinoid moieties.