| 间位苯基桥联的锰(Ⅲ)双咔咯的合成、表征及催化氧化性质 |
| Synthesis, Characterization and Catalytic Oxidation Activity of a Phenyl Bridged Dimanganese(Ⅲ) Biscorrole |
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| 摘要: 通过间苯二甲醛与5-氟苯基二吡咯甲烷反应合成了一种新的间位苯基桥联的双咔咯1，并利用锰盐与自由咔咯反应制备了其锰的金属配合物2.采用紫外、质谱、核磁、XPS等手段对化合物进行了表征。以苯乙烯为底物考察了锰双咔咯2的催化氧化性质，探讨了时间、溶剂、氧源、轴向配体对催化反应的影响。结果表明以亚碘酰苯和间氯过氧苯甲酸为氧源时催化的主要产物为环氧苯乙烷，而以双氧水和叔丁基过氧化氢为氧源时则主要产物为苯甲醛；在极性溶剂中的催化氧化产率较高。轴向配体对催化氧化有促进作用，不同轴向配体对催化反应产率提高的顺序是：1-甲基咪唑>吡啶>咪唑。 |
| 关键词: 双咔咯 锰 催化氧化 苯乙烯 轴向配体 |
| 基金项目: 国家自然基金（No.21171057，21371059）与广东省自然基金（No.10351064101000000）资助项目。 |
| Abstract: A m-phenyl bridged biscorrole 1 was synthesized by reaction of 1, 3-phthalaldehyde with 5-pentafluorophenyl dipyrromethane. The free base biscorrole was converted into its corresponding manganese complex 2 on reaction with a manganese salt. These compounds were characterized by UV-Vis, MS, NMR and XPS. The catalytic oxidation of manganese biscorrole complex 2 was investigated by using styrene as the substrate. The influence of reaction time, solvents, oxidants and axial ligands on the catalytic reaction was also examined. The results reveal that styrene epoxide is the major product when iodosylbenzene or m-chloroperoxybenzoic acid is used as the oxidant,while benzaldehyde is the major product when hydrogen peroxide or tert-butyl hydroperoxide is used as the oxidant. The percentage conversion is higher in polar solvents. The significant effect of axial ligand on the rate of catalytic oxidation is observed in the following order: 1-methylimidazole>pyridine>imidazole. |
| Keywords: biscorrole manganese catalytic oxidation styrene axial ligand |
| 投稿时间：2013-12-06 修订日期：2014-03-06 |
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| 陈欢,闻金燕,阳红,Mian HR Mahmood,章浩,刘海洋.间位苯基桥联的锰(Ⅲ)双咔咯的合成、表征及催化氧化性质[J].无机化学学报,2014,30(7):1725-1732. |
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