Catalytic Reactions with Soluble Metallophthalocyanines

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We prepared soluble metallophthalocyanine complexes by introducing substituents such as alkoxy groups on the phthalocyanine ring, and studied catalytic reactions with the complexes.The theams are as follows :[1] Preparation of one structural isomer of tetra-substitued phthalocyanine by controlling bulkiness of the substituents.[2] Chemical fixation of carbon dioxide by soluble phthalocyanine complexes.[3] Photoactivity of metallophthalocyanines.[4] Catalytic oxidation of olefin with metallophthalocyanines.[1] Using 3-pentoxyphthalonitrile as a starting material, one isomer of phthalocyanine was selectively prepared. The structure was determined by a X-ray crystal analysis. Some metal (II) complexes were prepared with the ligand, of which Zn (II) and Mg (II) complexes showed new additional peaks at 760 nm.[2] Cyclic propylene carbonate was prepared from CO_2 (1 atm) and propylene oxide in the presence of Al (III) complex at room temperature. Using the complex with Cl as an axial ligand, the fixation in the presence of 1-methylimidazole proceeds via sixcoordinate complex as an intermediate. With the complex in the presence of tetraethylammonium halide, the fixation proceeds via a six-ring member intermediate.[3] Methane was produced from CO_2 under irradiation with visible light using Zn (II) complex of trisulfophthalocyanine as a photocatalyst.[4] Stylene was oxidized to alcohol in the presence of NaBH_4 by molecular oxygen using Co (II), Mn (III) and Fe (III) complexes of tetra-t-butylphthalocyanine as the catalyst. The reaction mechanism is somewhat different between the Co (II) catalyst and Mn (III), Fe (III) catalysts.