کد مقاله کد نشریه سال انتشار مقاله انگلیسی نسخه تمام متن
1315817 1499424 2016 6 صفحه PDF دانلود رایگان
عنوان انگلیسی مقاله ISI
Visible light-induced formation of corrole-manganese(V)-oxo complexes: Observation of multiple oxidation pathways
موضوعات مرتبط
مهندسی و علوم پایه شیمی شیمی معدنی
پیش نمایش صفحه اول مقاله
Visible light-induced formation of corrole-manganese(V)-oxo complexes: Observation of multiple oxidation pathways
چکیده انگلیسی


• We report a new photochemical approach to produce corrole–manganese(V)-oxo complexes.
• We report kinetic and spectra studies of photo-generated manganese(V)-oxo corroles.
• We observe solvent and ligand effects on the reactivity of manganese(V)-oxo corroles.
• A mechanism involving multiple oxidation pathways is proposed and discussed.

Two manganese(V)-oxo corroles [MnV(Cor)O] that differ in their electronic environments were produced by visible light irradiation of highly photo-labile corrole-manganese(IV) bromates. The corrole ligands under study include 5,10,15-tris(pentafluorophenyl)corrole (TPFC), and 5,10,15-triphenylcorrole (TPC). The kinetics of oxygen transfer atom (OAT) reactions with various organic reductants by these photo-generated MnV(Cor)O were also studied in CH3CN and CH2Cl2 solutions. MnV(Cor)O exhibits remarkable solvent and ligand effect on its reactivity and spectral behavior. In the more electron-deficient TPFC system and in the polar solvent CH3CN, MnV(Cor)O returned MnIII corrole in the end of oxidation reactions. However, in the less polar solvent CH2Cl2 or in the less electron-deficient TPC system, MnIV product was formed instead of MnIII. Furthermore, with the same substrates and in the same solvent, the order of reactivity of MnV(Cor)O was TPC> TPFC, which is inverted from that expected based on the electron-demand of corrole ligands. Our spectral and kinetic results in this study provide compelling evidence in favor of multiple oxidation pathways, where MnV(Cor)O may serve as direct two-electron oxidant or undergo a disproportionation reaction to form a manganese(VI)-oxo corrole as the true oxidant. The choice of pathways is strongly dependent on the nature of the solvent and the corrole ligand.

Visible light irradiation of photo-labile corrole-manganese(IV) bromates efficiently produced corrole-manganese(V)-oxo complexes that oxidize organic substrates through different reaction pathways, depending on the corrole ligand and solvents.Figure optionsDownload as PowerPoint slide

ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Journal of Inorganic Biochemistry - Volume 163, October 2016, Pages 39–44
نویسندگان
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