Observation of Fe(V)=O using variable-temperature mass spectrometry and its enzyme-like C-H and C=C oxidation reactions

Nat Chem. 2011 Sep 4;3(10):788-93. doi: 10.1038/nchem.1132.

Abstract

Oxo-transfer chemistry mediated by iron underpins many biological processes and today is emerging as synthetically very important for the catalytic oxidation of C-H and C=C moieties that are hard to activate conventionally. Despite the vast amount of research in this area, experimental characterization of the reactive species under catalytic conditions is very limited, although a Fe(V)=O moiety was postulated. Here we show, using variable-temperature mass spectrometry, the generation of a Fe(V)=O species within a synthetic non-haem complex at -40 °C and its reaction with an olefin. Also, with isotopic labelling we were able both to follow oxygen-atom transfer from H(2)O(2)/H(2)O through Fe(V)=O to the products and to probe the reactivity as a function of temperature. This study pioneers the implementation of variable-temperature mass spectrometry to investigate reactive intermediates.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Alkenes / chemistry
  • Carbon / chemistry
  • Catalysis
  • Hydrogen / chemistry
  • Hydrogen Peroxide / chemistry
  • Iron / chemistry*
  • Isotope Labeling
  • Mass Spectrometry
  • Oxidation-Reduction
  • Oxides / chemistry*
  • Temperature
  • Thermodynamics

Substances

  • Alkenes
  • Oxides
  • perferryl iron
  • Carbon
  • Hydrogen
  • Hydrogen Peroxide
  • Iron

Associated data

  • PubChem-Substance/124807417
  • PubChem-Substance/124807418
  • PubChem-Substance/124807419
  • PubChem-Substance/124807420
  • PubChem-Substance/124807421
  • PubChem-Substance/124807422
  • PubChem-Substance/124807423
  • PubChem-Substance/124807424
  • PubChem-Substance/124807425
  • PubChem-Substance/124807426
  • PubChem-Substance/124807427
  • PubChem-Substance/124807428
  • PubChem-Substance/124807429
  • PubChem-Substance/124807430
  • PubChem-Substance/124807431
  • PubChem-Substance/124807432
  • PubChem-Substance/124807433
  • PubChem-Substance/124807434
  • PubChem-Substance/124807435
  • PubChem-Substance/124807436
  • PubChem-Substance/124807437
  • PubChem-Substance/124807438
  • PubChem-Substance/124807439
  • PubChem-Substance/124807440
  • PubChem-Substance/124807441
  • PubChem-Substance/124807442
  • PubChem-Substance/124807443
  • PubChem-Substance/124807444
  • PubChem-Substance/124807445
  • PubChem-Substance/124807446