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• W2011098025 abstract "The kinetics of bromide oxidation by several peroxo complexes of molybdenum(VI) and tungsten(VI) wre studied. All system obey the rate law d[Br+]/dt = k[etal complex][Br−]. At pH 1.0, we quantify the initial rate of bromine production by the spectrophotometric monitoring of the disappearance of fluorescein. The complexes and their rate constants at pH 1.0 and 25°C are MoO(O2)(ntal)− (nta = nitrilotriacelate (k = (1.64 ± 0.82) × 10−4 M−1s−1), MoO(O2)(dipic) (H2O (dipic = pyridine-2,6-dicarboxylate) k = (5.1 ± 0.2) × 10−4 M−1s−1), WO(O2)(dipic)H2O) k = (2.79 ± 0.02) × 10−2 M−1s−1), MoO(O2)2(pic)− (pic = pyridine-2-carboxylate) (k = (1.633 ± 0.001) × 10−1 M−1s−1 and MoO(O2)2(H2O)2 (k = 6.12 ± 0.03) × 10−1 M−1s−1. At pH 5.0, the initial rates were measured spectrophotometrically by the production of bromophenol blue from phenol red. The complexes and their rate constants at pH 5.0 and 25°C are MoO(O2)2(OH)(H2O)− (k = (8 ± 1) × 10−4 M−1s−1), WO(O2)2(OH)(H2O)− (k = (8.3 ± 0.7) × 10−3 M−1s−1) and WO(O2)2(C2O4)2− (k = (1.3 ± 0.2) × 10−2 M−1s−1). The 17O chemical shifts for the peroxo groups of MoO(O2)(ntal)− (501 ppm), MoO(O2)(dipic)(H2O) (537 ppm), WO(O2)(dipic)(H2O) (364 ppm), MoO(O2)2(pic)− (434 ppm) and WO(O2)2(C2O4)t– (368 ppm) were measured afte enrichment with H217O2. As expected, these values correlate with the reciprocal of the transition energies of the electronic spectra. The values ν(MoO) = 930 cm−1 and β(OO) = 900 cm−1 for MoO(O2)(nta)− are consistent with the vibrational features of similar compounds. The relationship between the spectroscopic properties and reactivity toward bromide oxidation follows previously observed patterns and may allow the reactivity of peroxometal complexes to be predicted from spectroscopic information." @default.
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• W2011098025 date "1997-10-01" @default.
• W2011098025 modified "2023-09-24" @default.
• W2011098025 title "Kinetics of bromide oxidation by peroxo complexes of molybdenum (VI) and tungsten (VI)" @default.
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• W2011098025 doi "https://doi.org/10.1016/s0020-1693(97)05658-2" @default.
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