A di‑iron(III) μ-oxido complex as catalyst precursor in the oxidation of alkanes and alkenes

Biswanath Das, Afnan Al-Hunaiti, Akina Carey, Sven Lidin, Serhiy Demeshko, Timo Repo, Ebbe Nordlander

Research output: Contribution to journalArticlepeer-review


The oxido-bridged diiron(III) complex [Fe2(μ-O)(μ-OAc)(DPEAMP)2](OCH3) (1), based on a new unsymmetrical ligand with an N4O donor set, viz. [2-((bis(pyridin-2-ylmethyl)amino)methyl)-6-((ethylamino)methyl)-4-methylphenol (HDPEAMP)], has been prepared and characterized by spectroscopic methods and X-ray crystallography. The crystal structure of the complex reveals that each Fe(III) ion is coordinated by three nitrogen and three oxygen donors, two of which are the bridging oxido and acetate ligands. Employing H2O2 as a terminal oxidant, 1 is capable of oxidizing a number of alkanes and alkenes with high activity. The catalytic oxidation of 1,2-dimethylcyclohexane results in excellent retention of configuration. Monitoring of the reaction of 1 with H2O2 and acetic acid in the absence of substrate, using low-temperature UV–Vis spectroscopy, suggests the in situ formation of a transient Fe(III)2-peroxido species. While the selectivity and nature of oxidation products implicate a high-valent iron-oxido complex as a key intermediate, the low alcohol/ketone ratios suggest a simultaneous radical-based process.

Original languageEnglish
Article number111769
JournalJournal of Inorganic Biochemistry
Publication statusPublished - 2022

Subject classification (UKÄ)

  • Inorganic Chemistry

Free keywords

  • Catalysis
  • Epoxidation
  • Hydroxylation
  • Iron
  • Metal-oxido complex
  • Peroxide complex


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