| 两种甲氧基苯基咔咯铜配合物的合成及光谱性质(英文) |
| Synthesis and Spectral Properties of Two Copper Methoxyphenylcorrole Complexes |
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| 摘要: 合成了两个中位苯基上具有甲氧基取代基的铜咔咯配合物(Tp-OCH3PC)Cu和(To，p-(OCH3)2PC)Cu，通过紫外-可见、红外光谱、元素分析、核磁共振及质谱对它们进行了表征。研究了配合物在非水溶剂中的电子顺磁共振、电化学和光谱电化学性质，结果表明无论在固体状态还是在非水溶剂中，配合物的中心金属离子均为三价铜Cu(Ⅲ)，在给定的溶剂中Cu(Ⅲ)可以发生可逆的还原反应生成Cu(Ⅱ)，也可以被可逆氧化为Cu(Ⅲ)的阳离子自由基。探讨了甲氧基取代基以及溶剂对配合物的紫外-可见光谱和氧化还原电位的影响。 |
| 关键词: 铜咔咯 合成 表征 电化学 光谱性质 |
| 基金项目: |
| Abstract: Two copper methoxyphenylcorrole complexes were synthesized and characterized by UV-Vis, FTIR, 1H NMR, MS and ESR spectroscopies. The investigated corroles are represented as (Tp-OCH3PC)Cu and (To, p-(OCH3)2PC)Cu, where Tp-OCH3PC and To, p-(OCH3)2PC are the trianion of the 5,10,15-tri(4-methoxyphenyl)corrole and 5,10,15-tri(2,4-dimethoxyphenyl)corrole, respectively. Neutral copper complexes expected to contain the low spin d8 Cu(Ⅲ) central ions exhibit no ESR signal in the solid state and in CH2Cl2 or DMF solutions, thin-layer UV-Visible spectroelectrochemistry result indicates that the first reduction of Cu(Ⅲ) corroles leads to formation of a Cu(Ⅱ) species in non-aqueous media while the first oxidation of the same compound is corrole ring-centered to give a Cu(Ⅲ) π-cation radical under the same solution conditions. Effects of the electron-donating OCH3 substituents and the solvent on the UV-Vis spectra and redox potentials of the copper corrole were discussed. |
| Keywords: copper(Ⅲ) corrole synthesis characterization electrochemistry spectral property |
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| 朱卫华,陈 晨,房媛媛,练翠翠,路桂芬,欧忠平.两种甲氧基苯基咔咯铜配合物的合成及光谱性质(英文)[J].无机化学学报,2011,27(12):2494-2500. |
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