Synergistic effects of CH3CO2H and Ca2+ on C-H bond activation by MnO4-

Research output: Journal Publications and ReviewsRGC 21 - Publication in refereed journalpeer-review

3 Scopus Citations
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Author(s)

  • Yi Pan
  • Chi-Keung Mak
  • Tai-Chu Lau

Related Research Unit(s)

Detail(s)

Original languageEnglish
Pages (from-to)11600-11606
Journal / PublicationChemical Science
Volume13
Issue number39
Online published13 Sept 2022
Publication statusPublished - 21 Oct 2022

Link(s)

Abstract

The activation of metal-oxo species with Lewis acids is of current interest. In this work, the effects of a weak Brønsted acid such as CH3CO2H and a weak Lewis acid such as Ca2+ on C-H bond activation by KMnO4 have been investigated. Although MnO4- is rather non-basic (pKa of MnO3(OH) = -2.25), it can be activated by AcOH or Ca2+ to oxidize cyclohexane at room temperature to give cyclohexanone as the major product. A synergistic effect occurs when both AcOH and Ca2+ are present; the relative rates for the oxidation of cyclohexane by MnO4-/AcOH, MnO4-/Ca2+ and MnO4-/AcOH/Ca2+ are 1 : 73 : 198. DFT calculations show that in the active intermediate of MnO4-/AcOH/Ca2+, MnO4- is H-bonded to 3 AcOH molecules, while Ca2+ is bonded to 3 AcOH molecules as well as to an oxo ligand of MnO4-. Our results also suggest that these synergistic activating effects of a weak Brønsted acid and a weak Lewis acid should be applicable to a variety of metal-oxo species.

Research Area(s)

  • ELECTRON-TRANSFER REACTIVITY, METAL-ION, OXYGEN-TRANSFER, OXIDATION, ACID, COMPLEXES, MECHANISM, ALKANES, PERMANGANATE, LEWIS

Citation Format(s)

Synergistic effects of CH3CO2H and Ca2+ on C-H bond activation by MnO4-. / Shi, Huatian; Cheng, Lin; Pan, Yi et al.
In: Chemical Science, Vol. 13, No. 39, 21.10.2022, p. 11600-11606.

Research output: Journal Publications and ReviewsRGC 21 - Publication in refereed journalpeer-review

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