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- W2037161750 abstract "The metal bound superoxide in μ-superoxo-bis[pentaamminecobalt(III)]5+ (1) oxidizes the nitrosodisulfonate anion radical (NDS2−) by two electrons. Oxidized NDS2− quickly decomposes to SO42− and NO. 1 is itself reduced to the corresponding hydroperoxo complex which also decomposes fast to Co(II), NH4+ ions and oxygen. 1.5 moles of volatile products formed per mole of 1 mixed with excess NDS2−. In the absence of superoxide in a bridged complex, e.g. the μ-amido-bis[pentaamminecobalt(III)]5+ complex fails to oxidize the nitroxyl radicals, NDS2−, TEMPO and 4-oxo TEMPO. With excess NDS2− over 1, the reaction is first-order with respect to [1], [NDS2−] and inverse first order in [H+]. The activation entropy, ΔS≠, is largely negative, increased ionic strength decreased the rate and a Brønsted plot is fairly linear with a negative slope. Oxidant μ-superoxo-bis[(ethylenediamine)(diethylenetriamine)cobalt(III)]5+ has ligands sterically more crowded though more basic than ammonia in 1. It oxidizes NDS2− much more slowly. No solvent kinetic isotope effect (kH2O/D2O ≈ 1) could be seen; a spin-adduct formation by the conjugate base of 1 followed by electron transfer is postulated." @default.
- W2037161750 created "2016-06-24" @default.
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- W2037161750 date "2012-01-01" @default.
- W2037161750 modified "2023-10-16" @default.
- W2037161750 title "Kinetics of oxidation of nitrosodisulfonate anion radical with a metallo-superoxide" @default.
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- W2037161750 doi "https://doi.org/10.1039/c2dt12019d" @default.
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