Base-promoted perfluoroalkylation of rhodium() porphyrin complexes

A new family of rhodium porphyrin complexes bearing a primary, secondary or benzylic perfluoroalkyl ligand Rh III (btpp)R F [btpp = 5,10,15,20-tetrakis(4- tert -butylphenyl)porphyrinato dianion] has been successfully synthesized in good yields using commercially available perfluoroalkyl iodides R F I (R F = n C 3 F 7 , i C 3 F 7 , n C 4 F 9 , n C 6 F 13 , c C 6 F 11 , n C 10 F 21 and C 6 F 5 CF 2 ) and the air-stable precursor Rh III (btpp)Cl under basic conditions. Mechanistic investigations suggest a halogen atom transfer pathway with a rhodium( ii ) porphyrin metalloradical. The syntheses of primary, secondary and benzylic perfluoroalkyl rhodium( iii ) porphyrin complexes are described.