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近年来,化学家们对高价锰卟啉配合物的合成非常感兴趣。高价锰卟啉配合物在温和条件下分解水,释放氧,是植物光体系Ⅱ的可能的模型化合物。锰卟啉配合物在比较温和条件下活化分子氧,选择性地催化氧化碳氢化合物,是单加氧酶细胞色素P-450的很好的模型体系。由于缺少已合成的高价锰卟啉配合物,所以植物光体系Ⅱ和细胞色素P-450模型体系的活性中间体的研究遇到了障碍。Hill等在氯苯中用氧化碘苯氧化XMn(Ⅲ)TPP(TPP=四苯基卟啉基),合成了两类双核的四价锰四苯基卟啉配合物,[XMnⅣ)TPP]_2O(X=N_3~-或OCN~-)和[XMn(Ⅳ)TPP(OIPh)]_2O(X=Cl~-或Br~-,OIPh=氧化碘苯)。但还未能合成出单核的氧化碘苯锰(Ⅳ)四苯基卟啉配合物。我们选择位阻大于Cl~-、Br~-、N_3~-和OCN~-,键合能力介于Cl~-、Br~-与N_3~-、OCN~-之间的间氨基苯甲酸作为轴向配体,成功地合成了单核的m-H_2NC_6H_4CO_2Mn(Ⅳ)TPP(OIPh)(1),并讨论了它的光谱性质。
In recent years, chemists are very interested in the synthesis of expensive manganese porphyrin complexes. High molecular weight porphyrin complexes decompose water under mild conditions and release oxygen, which is a possible model compound for photosystem II of plants. Manganese porphyrin complex activates molecular oxygen under mild conditions and selectively catalyzes the oxidation of hydrocarbons, which is a good model system for monooxygenase cytochrome P-450. Due to the lack of the synthesized high-valent porphyrin complexes, studies on the active intermediates of plant photosystem Ⅱ and cytochrome P-450 model system have encountered obstacles. Hill and other chlorobenzene iodine oxidation with iodine oxidation of XMn (TPP) (TPP = tetraphenylporphyrin), two types of binuclear tetravalent manganese tetraphenylporphyrin complexes, [XMnⅣ) TPP] _2O (X═N_3 ~ - or OCN ~ -) and [XMn (Ⅳ) TPP (OIPh)] _2O (X = Cl ~ - or Br ~ -, OIPh = iodobenzene oxide). However, mononuclear oxidized iodobenzene manganese (IV) tetraphenylporphyrin complexes have not been synthesized yet. We chose m-aminobenzoic acid with a higher blocking capacity than Cl ~ -, Br ~ -, N_3 ~ - and OCN ~ -, with Cl ~ -, Br ~ - and N_3 ~ The mononuclear m-H 2 NC 6 H 4 CO 2 Mn (IV) TPP (OIPh) (1) was successfully synthesized and its spectral properties were discussed.