Mechanistic study for the selective oxidation of benzene and toluene catalyzed by Fe(ClO4)2 in an H2O2-H2O-CH3CN system

Ravirala Ramu, Wondemagegn Hailemichael Wanna, Damodar Janmanchi, Yi Fang Tsai, Chih Cheng Liu, Chung Yuan Mou, Steve S.F. Yu

Research output: Contribution to journalArticlepeer-review

18 Citations (Scopus)

Abstract

Iron(II) perchlorate in an H2O-H2O2-CH3CN mixture was used to efficiently carry out C–H bond activations of benzene to form phenol and/or hydroquinone, and of toluene to form benzaldehyde, benzyl alcohol, o-cresol, p-cresol, and/or methyl-p-benzoquinone. The reactions were facilely tuned and controlled to selectively yield either a single or double oxygenation of benzene as well as a sp3 or sp2 C–H bond oxidation of toluene. On the basis of H/D kinetic isotope effect data, we determined the aromatic oxidation to mostly proceed by way of formation of an arene oxide or a σ-complex intermediate from high-valence iron species and to then undergo a 1,2-hydride shift, i.e., NIH-shift rearrangement.

Original languageEnglish
Pages (from-to)114-121
Number of pages8
JournalMolecular Catalysis
Volume441
DOIs
Publication statusPublished - 2017
Externally publishedYes

Keywords

  • Chain hydroxylation
  • Hydrogen peroxide
  • Iron(II) perchlorate
  • Kinetic isotope effect
  • Oxidation
  • Ring hydroxylation
  • Selectivity

ASJC Scopus subject areas

  • Catalysis
  • Process Chemistry and Technology
  • Physical and Theoretical Chemistry

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