New alkyl substituted phosphorus phthalocyanines and triazatetrabenzocorroles were syn thesized. The structures of these complexes were confirmed by 1 H, 13 C, and 31 P NMR spec troscopy, mass spectrometry, and electronic absorption spectroscopy.Methods for the synthesis and properties of various metal phthalocyanines having both planar and sandwich structures have been studied in sufficient detail, whereas phthalocyanine complexes with nonmetals have received much less attention. In our previous study, 1 we have in vestigated boron phthalocyanine complexes. Due to the small radius, boron is prone to form only subphthalo cyanine complexes with ligands consisting of three iso indole fragments. Due to the geometric and electronic structures, these complexes exhibit unusual spectroscopic properties allowing their use in new fields of engineering.The aim of the present study was to synthesize alkyl substituted phosphorus phthalocyanines and triazatetra benzocorroles and investigate their spectroscopic prop erties.Phosphorus phthalocyanines were synthesized for the first time 2 in 1981. However, data on these compounds are scarce, and many questions remain open.It was reported that phosphorus can form not only phthalocyanine complexes but also complexes with tri azatetrabenzocorroles. 3,4 Initially, it has been hypoth esized that the latter compounds are phthalocyanine com plexes of trivalent phosphorus. 2 However, further physi cochemical studies showed that the complex consists of triazatetrabenzocorrole and pentavalent phosphorus; ana logs of this complex are synthesized for both nonmetals (germanium and silicon) and some metals (manganese, iron, and chromium). 5 The electronic structure of tri azatetrabenzocorrole, whose "window" radius allows sta bilization of the complexing ions in high oxidation states, can favor the use of these compounds in oxidative ca talysis.
Results and DiscussionWe used metal free phthalocyanines 1 and 2, which have been prepared in our earlier study, 6 as the starting compounds for the synthesis of phosphorus phthalocya nine and triazatetrabenzocorrole complexes, respectively. Depending on the nature of the starting phosphorus con taining compound, the reactions give different types of complexes. The reactions of phosphorus(v) oxyhalides produce phthalocyanine complexes, whereas the reac tions of phosphorus(III) bromide give triazatetrabenzo corroles (Scheme 1).In the reaction with PBr 3 for 1.5 h, phthalocyanine 1 undergoes complete conversion to form the only product of the phthalocyanine nature, viz., triazatetrabenzocor role (3). Since compound 3 is poorly soluble in most of organic solvents, investigations of 3 present difficulties. The use of tert butyl substituted phthalocyanine (2) as the starting compound allowed us to substantially increase the solubility of the resulting triazatetrabenzocorrole 4.The reaction of phthalocyanine 2 with POCl 3 giving rise to compound 6 was completed in 24 h. The yield of the product was 62%. The reaction time in the case of POBr 3 decreases to 4...