Base-promoted perfluoroalkylation of rhodium(iii) 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 RFI (R-F = (C3F7)-C-n, (C3F7)-C-i, (C4F9)-C-n, (C6F13)-C-n, (C)C6F11, (C10F21)-C-n 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.

Automated summary

A new family of rhodium porphyrin complexes with various perfluoroalkyl ligands has been successfully synthesized in good yields using commercially available perfluoroalkyl iodides and the air-stable precursor, suggesting a halogen atom transfer pathway with a rhodium(ii) porphyrin metalloradical through mechanistic investigations.