Base-promoted perfluoroalkylation of rhodium(iii) porphyrin complexes

Abstract

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_FI (R_F = ⁿC₃F₇, ⁱC₃F₇, ⁿC₄F₉, ⁿC₆F₁₃, ^cC₆F₁₁, ⁿC₁₀F₂₁ and C₆F₅CF₂) 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.