کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
---|---|---|---|---|
1309123 | 1499159 | 2015 | 8 صفحه PDF | دانلود رایگان |
![عکس صفحه اول مقاله: A biomimetic oxidation catalyzed by manganese(III) porphyrins and iodobenzene diacetate: Synthetic and mechanistic investigations A biomimetic oxidation catalyzed by manganese(III) porphyrins and iodobenzene diacetate: Synthetic and mechanistic investigations](/preview/png/1309123.png)
• We report a biomimetic oxidation by manganese(III) porphyrins and PhI(OAc)2.
• We demonstrate the synthetic utility by investigating the reaction conditions and scope.
• We present the mechanistic studies including competition, kinetic and spectra studies.
• We propose a high-valent manganese(V)-oxo intermediate as the active oxidant.
With iodobenzene diacetate [PhI(OAc)2] as the oxygen source, manganese(III) porphyrin complexes exhibit remarkable catalytic activity toward the selective oxidation of alkenes and activated hydrocarbons. Conspicuous is the fact that the readily soluble PhI(OAc)2 in the presence of a small amount of water is more efficient than the commonly used PhIO and other oxygen sources under same catalytic conditions. High selectivity for epoxides and excellent catalytic efficiency with up to 10,000 TON have been achieved in alkene epoxidations. It was found that the reactivity of manganese(III) porphyrin catalysts was greatly affected by axial ligand and the weakly binding perchlorate gave the highest catalytic activity in the epoxidation of alkenes. A manganese(IV)-oxo porphyrin was detected in the reaction of the manganese(III) porphyrin and PhI(OAc)2. However, our catalytic competition and Hammett studies have suggested that the more reactive manganese(V)-oxo intermediate was favored as the premier active oxidant, even it is too short-lived to be produced in detectable concentrations.
Synthetic and mechanistic studies of a biomimetic oxidation catalyzed by manganese(III) porphyrins and iodobenzene diacetate are reported.Figure optionsDownload as PowerPoint slide
Journal: Inorganica Chimica Acta - Volume 430, 1 May 2015, Pages 176–183