Syntheses and photochemistry of fluorinated and chlorinated titanium porphyrinates: Crystal structure of oxotitanium meso-tetrakis(2,3,4,5,6-pentafluorophenyl)porphyrinate

The syntheses of oxotitanium(IV) meso-tetrakis(2,3,4,5,6-pentafluorophenyl)porphyrinate O=Ti(TPPF20) (1), oxotitanium(IV) meso-tetrakis(2,6-difluorophenyl)porphyrinate O=Ti(TPPF8) (3), and oxotitanium(IV) meso-tetrakis(2,6-dichlorophenyl)porphyrinate O=Ti(TPPCl8) (5) from titanium tetrachloride and the corresponding porphine are described. The structure of 1 was determined by single-crystal X-ray diffraction. The reaction of oxotitanium porphyrinates with aqueous hydrogen peroxide leads to the corresponding light-sensitive peroxotitanium(IV) complexes: Ti(O-2)(TPPF20) (2), Ti(O-2)(TPPF8) (4), Ti(O-2)(TPPCl8) (6). All complexes are efficient and stable photosensitizers for the generation of singlet oxygen.