4.7 Article

A hydrogen-atom transfer mechanism in the oxidation of alcohols by [FeO4]2- in aqueous solution

Journal

DALTON TRANSACTIONS
Volume 47, Issue 1, Pages 240-245

Publisher

ROYAL SOC CHEMISTRY
DOI: 10.1039/c7dt03830e

Keywords

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Funding

  1. Hong Kong University Grants Committee Areas of Excellence Scheme [AoE/P-03/08]
  2. Research Grants Council of Hong Kong [CityU 101713, 11301514]

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The ferrate(VI) ion, [FeO4](2-), has attracted much interest in recent years because of its potential use as a green oxidant in organic synthesis and water treatment. Although there have been several reports on the use of ferrate(VI) for the oxidation of alcohols to the corresponding carbonyl compounds, the mechanism remains unclear. In this work, the kinetics of the oxidation of a series of alcohols with alpha-C-H bond dissociation energies ranging from 81 to 95 kcal mol(-1) have been studied by UV/Vis spectrophotometry. The reactions are first-order in both [FeO4](2-) and [alcohol]. The deuterium isotope effects for the oxidation of methanol/d(4)-methanol, ethanol/d(6)-ethanol and benzyl alcohol/d(7)-benzyl alcohol are 18.0 +/- 0.1, 4.1 +/- 0.1 and 11.2 +/- 0.1, respectively. A linear correlation is found between the second-order rate constants and the alpha-C-H bond dissociation energies (BDEs) of the alcohols, consistent with a hydrogen atom transfer (HAT) mechanism. The proposed HAT mechanism is supported by DFT calculations.

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