Base-promoted perfluoroalkylation of rhodium(III) porphyrin complexes.

A new family of rhodium porphyrin complexes bearing a primary, secondary or benzylic perfluoroalkyl ligand RhIII(btpp)RF [btpp = 5,10,15,20-tetrakis(4-tert-butylphenyl)porphyrinato dianion] has been successfully synthesized in good yields using commercially available perfluoroalkyl iodides RFI (RF = nC3F7, iC3F7, nC4F9, nC6F13, cC6F11, nC10F21 and C6F5CF2) and the air-stable precursor RhIII(btpp)Cl under basic conditions. Mechanistic investigations suggest a halogen atom transfer pathway with a rhodium(ii) porphyrin metalloradical.