稳定 20π 异佛尔酮的还原形成并分离四电子还原卟啉衍生物
Formation and Isolation of a Four-Electron-Reduced Porphyrin Derivative by Reduction of a Stable 20π Isophlorin.
机构信息
Department of Chemistry, Graduate School of Pure and Applied Sciences, University of Tsukuba, 1-1-1 Tennoudai Tsukuba, Ibaraki, 305-8571, Japan.
Institute for Materials Chemistry and Engineering, Kyushu University, Motooka, Nishi-Ku, Fukuoka, 819-0395, Japan.
出版信息
Angew Chem Int Ed Engl. 2018 Feb 12;57(7):1973-1977. doi: 10.1002/anie.201711058. Epub 2018 Jan 16.
The two-electron reduction of a diprotonated dodecaphenylporphyrin derivative by Na S O gave a corresponding isophlorin (Iph) selectively. Formation of Iph was confirmed by spectroscopic measurements and the isolation of tetramethylated Iph. Further reduction of Iph proceeded to form an unprecedented four-electron-reduced porphyrin (IphH ), which was fully characterized by spectroscopic and X-ray crystallographic analysis. IphH , with a unique conformation, could be oxidized to reproduce the starting porphyrin, resulting in a proton-coupled four-electron reversible redox system.
双质子化的十二苯基卟啉衍生物在亚硫酸钠的作用下，可选择性地得到相应的异佛洛林（Iph）。通过光谱测量和四甲基化 Iph 的分离证实了 Iph 的形成。Iph 的进一步还原生成了一种前所未有的四电子还原卟啉（IphH），其结构通过光谱和 X 射线晶体学分析得到了充分的表征。IphH 具有独特的构象，可以被氧化以再生起始卟啉，从而形成质子耦合的四电子可逆氧化还原体系。
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