کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
---|---|---|---|---|
10244434 | 47685 | 2005 | 7 صفحه PDF | دانلود رایگان |
عنوان انگلیسی مقاله ISI
Kinetics and mechanism of cyclohexane oxidation catalyzed by supramolecular manganese(III) porphyrins
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کلمات کلیدی
موضوعات مرتبط
مهندسی و علوم پایه
مهندسی شیمی
کاتالیزور
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چکیده انگلیسی
We report the kinetics of cyclohexane oxidation with iodosylbenzene, catalyzed by two supramolecular manganese(III) porphyrin isomers, containing four [Ru(bpy)2Cl]+ complexes attached to the pyridyl groups of meso-tetra(3-pyridyl)porphynatemanganese(III) or meso-tetra(4-pyridyl)porphynatemanganese(III) centers. An unusual pseudozero-order mechanism was observed by monitoring the formation of the cyclohexanol and cyclohexanone products, and a consistent oxygen-transfer mechanism, activated by the manganese center, was proposed on the light of the kinetic behavior. The kH/kD values suggested that in Mn(3-TRPyP) catalysis, the kinetics are favored by the stereochemical environment provided by the out-of-plane ruthenium complexes, whereas for the coplanar Mn(4-TRPyP) catalyst, the favorable electronic interaction of the ruthenium complexes with the metalloporphyrin center is the most relevant factor enhancing reactivity.
ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Journal of Catalysis - Volume 236, Issue 1, 15 November 2005, Pages 55-61
Journal: Journal of Catalysis - Volume 236, Issue 1, 15 November 2005, Pages 55-61
نویسندگان
Genebaldo S. Nunes, Ildemar Mayer, Henrique E. Toma, Koiti Araki,