Catalytic Reactions with Soluble Metallophthalocyanines

我们通过在酞菁环上引入烷氧基等取代基制备了可溶的金属酞菁配合物，并对其催化反应进行了研究。主要内容如下：[1]通过控制取代基的体积制备了一个四取代的结构异构体；[2)通过控制取代基的体积制备了一个结构异构体；[2)通过可溶络合物对二氧化碳的化学固定；[3)金属酞菁的光活性；[4]金属酞菁对烯烃的催化氧化。[1]以3-戊氧基邻苯二甲腈为起始原料，选择性地合成了一个结构异构体。通过X射线晶体分析确定了该化合物的结构。用该配体制备了一些金属(II)配合物，其中锌(II)和镁(II)的配合物在760 nm处出现了新的附加峰。[2]在Al(III)的存在下，CO_2(1 Atm)和环氧丙烷在室温下合成了环状碳酸亚丙酯。以含氯的络合物为轴向配体，在1-甲基咪唑存在下，以六配位络合物为中间体进行固定。在四乙基卤化铵存在下，该络合物通过六环中间体进行固定。[3]CO_2在可见光照射下，以三磺酸锌络合物为光催化剂由CO_2生成甲烷。[4]在NaBH_4存在下，以Co(II)、Mn(III)和Fe(III)为催化剂，分子氧将苯乙烯氧化为乙醇。Co(II)催化剂与Mn(III)、Fe(III)催化剂的反应机理略有不同。

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.