Electrooxidation of porphyrin free bases:: fate of the π-cation radical

被引:72
|
作者
Inisan, C
Saillard, JY
Guilard, R
Tabard, A
Le Mest, Y
机构
[1] Univ Bretagne Occidentale, Lab Chim Electrochim Mol & Chim Analyt, CNRS, UMR 6521, F-29285 Brest, France
[2] Univ Rennes 1, Chim Solide & Inorgan Mol Lab, CNRS, UMR 6511, F-35042 Rennes, France
[3] Univ Bourgogne, Fac Sci Gabriel, LIMSAG, CNRS,UMR 5633, F-21100 Dijon, France
关键词
D O I
10.1039/a803974g
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
In contrast to metalloporphyrins with non-electroactive metal centres, the pi-cation radicals of porphyrin free bases (H2OEP, H2TPP, H(2)CdiE) electrogenerated in strictly anhydrous solvents are not stable and give rise to a quantitative chemical reaction. Conjunction of electrochemical and spectroscopic data (UV/VIS, EPR and NMR) demonstrates unambiguously that the porphyrin skeleton is not modified during the chemical reaction. The reaction product is the protonated free base, and thus the free base can be regenerated by reduction of the protons.
引用
收藏
页码:823 / 830
页数:8
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