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- W1997376774 abstract "The superoxochromium complex CraqOO2+ abstracts a hydrogen atom from CMe3CHO in acidic aqueous solution with k = 0.16 M-1 s-1. This rate constant is only ∼102 times smaller than that for the reaction of CraqO2+ with the same aldehyde, k = 23 M-1 s-1, in contrast to the much greater reactivity difference between alkoxyl and alkylperoxyl radicals, kt-BuO/kt-BuOO ≈ 106. The absolute rate constants for hydrogen atom abstraction from a common reagent by metal-oxo and -superoxo species and the corresponding organic oxygen-centered radicals, RO• and ROO•, can now be compared for the first time: kBuO (9 × 107 M-1 s-1) > kCrO(23) ≥ kBuOO(8) > kCrOO (0.16). The reactivity of individual species is explained by the energetics of the O−H bonds in ROH, ROOH, CraqOH2+, and CraqOOH2+." @default.
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- W1997376774 date "2000-02-01" @default.
- W1997376774 modified "2023-09-27" @default.
- W1997376774 title "Hydrogen Atom Abstraction by Metal−Oxo and Metal−Superoxo Complexes: Kinetics and Thermodynamics" @default.
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- W1997376774 doi "https://doi.org/10.1021/ja993371s" @default.
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