Studies on phosphorus phthalocyanines and triazatetrabenzcorroles

The previously reported reaction of phthalocyanines [H-2(pc)] with PBr3, wh ich was claimed to give a phosphorus(III) phthalocyanine "(PcPIII)", has be en reinvestigated in detail with both unsubstituted and alkyl-substituted p hthalocyanines, 1-4. The products exhibit unusual electronic and mass spect ra compared to normal phthalocyanines and have been identified as oxophosph orus(V) triazatetrabenzcorroles 5-8. The corresponding dihydroxyphosphorus( V) phthalocyanine hydroxides 9-12 have also been synthesized for the first time by insertion of phosphorus(V) into phthalocyanines and have been chara cterized in detail. The different reactivities of PBr3 and POX3 (X = Cl, Br ) toward phthalocyanines are discussed.