Akhssas Fatima, Lin Rongning, Trojan Michal, Poyac Ludivine, Amiri Nesrine, Ertel Thibault, Fournier Sophie, Lerayer Emmanuel, Cattey Hélène, Clément Sébastien, Richeter Sébastien, Devillers Charles H
Institut de Chimie Moléculaire de l'Université de Bourgogne UMR6302, CNRS, Univ. Bourgogne, 9 avenue Alain Savary, 21000, Dijon, France.
Department of Organic Chemistry, University of Chemistry and Technology, Prague, Technická 5, Prague 6, 166 28, Czech Republic.
ChemSusChem. 2024 Dec 20;17(24):e202401439. doi: 10.1002/cssc.202401439. Epub 2024 Oct 22.
Electrochemical oxidation of Zn(II) 2,7,12,17-tetra-tert-butylporphyrin in the presence of a series of azole derivatives (1-methylimidazole, 1-vinyl-1H-imidazole, 2-(1H-imidazol-1-yl)pyridine, 1-methylbenzimidazole, 1-methyl-1H-1,2,4-triazole, and benzothiazole) affords the corresponding meso-substituted azolium-porphyrins in very mild conditions and good yields. It was found that these nucleophiles were strongly ligated to the zinc(II) azolium-porphyrin complexes. Thus a demetalation/remetalation procedure was performed to recover the non-azole-coordinated zinc(II) complexes. X-ray crystallographic structures of three azolium-porphyrins were solved. Cyclic voltammetry analyses provided insight into the electron-withdrawing effect of the azolium substituents.
在一系列唑衍生物（1-甲基咪唑、1-乙烯基-1H-咪唑、2-(1H-咪唑-1-基)吡啶、1-甲基苯并咪唑、1-甲基-1H-1,2,4-三唑和苯并噻唑）存在下，对 Zn(II) 2,7,12,17-四叔丁基卟啉进行电化学氧化，可在非常温和的条件下以良好的产率得到相应的中位取代唑鎓-卟啉。研究发现，这些亲核试剂与锌(II)唑鎓-卟啉配合物强烈配位。因此，进行了脱金属/再金属化过程以回收未与唑配位的锌(II)配合物。解析了三种唑鎓-卟啉的 X 射线晶体结构。循环伏安法分析深入了解了唑鎓取代基的吸电子效应。
