Preparation and characterization of manganese(IV) in aqueous acetic acid

TitlePreparation and characterization of manganese(IV) in aqueous acetic acid
Publication TypeJournal Article
Year of Publication2010
AuthorsJee JE, Pestovsky O, Bakac A
Journal TitleDalton Transactions
Date Published12/28
ISBN Number1477-9226
Accession NumberISI:000284777500018
KeywordsAUTOXIDATION, bromide, HYDROCARBONS, kinetics, mononuclear manganese(iv), oxidation, oxygen, P-XYLENE, paramagnetic-susceptibility, precipitation

Mn(IV) acetate was generated in acetic acid solutions and characterized by UV-vis spectroscopy, magnetic susceptibility, and chemical reactivity. All of the data are consistent with a mononuclear manganese(IV) species. Oxidation of several substrates was studied in glacial acetic acid (HOAc) and in 95 : 5 HOAc-H2O. The reaction with excess Mn(OAc)(2) produces Mn(OAc)(3) quantitatively with mixed second-order kinetics, k (25.0 degrees C) = 110 +/- 4 M-1 s(-1) in glacial acetic acid, and 149 +/- 3 M-1 s(-1) in 95% AcOH, Delta H double dagger = 55.0 +/- 1.2 kJ mol(-1), Delta S double dagger = -18.9 +/- 4.1 J mol(-1) K-1. Sodium bromide is oxidized to bromine with mixed second order kinetics in glacial acetic acid, k = 220 +/- 3 M-1 s(-1) at 25 degrees C. In 95% HOAc, saturation kinetics were observed.

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Alternate JournalDalton T