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Catalytic Reactions with Soluble Metallophthalocyanines

与可溶性金属酞菁的催化反应

基本信息

批准号：
06453050
负责人：
KASUGA Kuninobu
金额：
$ 4.8万
依托单位：
Shimane University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
1994
资助国家：
日本
起止时间：
1994 至 1996
项目状态：
已结题

项目摘要

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.

通过在酞菁环上引入烷氧基等取代基，制备了可溶性金属酞菁配合物，并研究了其催化反应，主要研究结果如下：[1]通过控制取代基的体积，制备了一种四取代酞菁结构异构体。[2]可溶性酞菁配合物对二氧化碳的化学固定。[3]金属酞菁的光活性。[4]金属酞菁催化氧化烯烃。[1]以3-戊氧基邻苯二甲腈为原料，选择性地合成了一种酞菁异构体。通过X射线晶体分析确定结构。用该配体制备了一些金属（II）配合物，其中Zn（II）和Mg（II）配合物在760 nm处出现了新的吸收峰。[2]室温下，在Al（III）配合物的存在下，以CO2（1atm）和环氧丙烷为原料合成了环状碳酸丙烯酯。以氯离子为轴向配体，在1-甲基咪唑存在下，通过六配位络合物作为中间体进行固定。在四乙基卤化铵存在下，通过六元环中间体进行固定。[3]以邻苯三磺酸锌配合物为光催化剂，在可见光照射下，以CO_2为原料合成甲烷。[4]以四叔丁基酞菁的Co（II）、Mn（III）、Fe（III）配合物为催化剂，在NaBH_4存在下，用分子氧氧化苯乙烯合成醇。Co（II）催化剂与Mn（III）、Fe（III）催化剂的反应机理有所不同。