A kinetic electron spin resonance study of the reaction of some oxy radicals with vanadyl acetylacetonate

Autor:	James A. Howard, J. H. B. Chenier, John Charles Tait, T. Yamada
Rok vydání:	1981
Předmět:	Chemistry Radical Organic Chemistry Nitroxyl General Chemistry Photochemistry Catalysis law.invention Reaction rate chemistry.chemical_compound Galvinoxyl law Kinetic isotope effect Reactivity (chemistry) Vanadyl acetylacetonate Electron paramagnetic resonance
Zdroj:	Canadian Journal of Chemistry. 59:2184-2190
ISSN:	1480-3291 0008-4042
DOI:	10.1139/v81-315
Popis:	Reactions of phenoxyl, iminoxyl, nitroxyl, peroxyl, and alkoxyl radicals with VO(acac)2 in solution have been studied by kinetic esr spectroscopy. Rates of reaction are first-order with respect to each reactant and radical reactivity increases in the order galvinoxyl 3OH is replaced by deuterium. Vanadium-51 nmr spectroscopy has demonstrated that several vanadium(V) products are formed while conventional product studies have indicated that, in the case of phenoxyl and alkoxyl, the radical is reduced almost exclusively to the parent phenol and alcohol and that VO(acac)2 is eventually regenerated in substantial yields. The net reaction is, therefore, catalytic reduction of the radical. Variable temperature esr studies have shown that phenoxyl and iminoxyl radicals and VO(acac)2 exist in equilibrium with diamagnetic reaction products.
Databáze:	OpenAIRE
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