Octaarylsubstituted Si(IV) Porphyrazine and Corrolazine: Synthesis by Complexation Method and Formation of μ-Oxo Dimers

The reaction of octaphenylporphyrazine with trichlorosilane in pyridine produces dihydroxysilicon octaphenylporphyrazine (HO) 2 SiPzPh 8 in 75% yield.This method has been shown to be more efficient than the previously used tetramerization of the corresponding diiminoimide in the presence of SiCl 4 .When refluxing in dry pyridine in the presence of tributylchlorosilane (Bu 3 SiCl) and tributylamine as a base the axial substitution with formation of (Bu 3 SiO) 2 SiPzPh 8 is observed.Under action of Mg-Bu 3 SiCl system the porphyrazine macrocycle undergoes reductive contraction with formation of corrolazine (Bu 3 SiO)SiCzPh 8 .Treatment of corrolazine complexes (Alk 3 SiO)SiCzPh 8 and (Alk 3 SiO)SiCz( t BuPh) 8 (Alk=Pr or Bu) by hydrofluoric acid results in formation of corresponding fluoride derivatives.When attempting to separate them by column chromatography on aluminum oxide (CH 2 Cl 2 :CH 3 OH = 98:2), formation of μ-oxo dimers O[SiAr 8 ] 2 most likely occurs.