ИСТИНА

Ruthenium complexes with phthalocyanine ligands (RuPc) can be considered as close analogues of iron porphyrins which constitute active sites of hemoproteins and play crucial roles in the transfer of small molecules and oxidation of organic substrates in Nature. However, the catalytic chemistry of RuPc is much less developed as compared with their iron counterparts. Development of new synthetic approaches to access novel RuPc structures and investigation of their properties are therefore the important tasks. Although ruthenium phthalocyaninates are commonly synthesized by template condensation of phthalonitriles in the presence of the metal source [1], here we report a detailed investigation of the direct metalation of the preformed substituted phthalocyanines to broaden the scope of complexes with the required properties. The interaction between Ru3(CO)12 and various phthalocyanine ligands 1a-d in odichlorobenzene at 180°C unexpectedly yielded simultaneously two types of complexes – monomeric carbonyl phthalocyaninatoruthenium(II) 2a-d and dimeric μ-carbido-bridged bis[(phthalocyaninatoruthenium(IV)] 3a-c, which have been separated by size-exclusion chromatography and characterized by UV-Vis, NMR, FT-IR, MALDI TOF and HR-ESI MS. The yield of dimeric species gradually decreased upon the increase of bulkiness of the substituents at the Pc periphery. The dimer 3d with the most bulky mesityloxy-groups could not be obtained under these conditions.