Axial ligand substituted nonheme FeIV=O complexes: observation of near-UV LMCT bands and Fe=O Raman vibrations

J Am Chem Soc. 2005 Sep 14;127(36):12494-5. doi: 10.1021/ja0540573.

Abstract

Axial ligand substitution of a mononuclear nonheme oxoiron(IV) complex, [FeIV(O)(TMC)(NCCH3)]2+ (1) (TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane), leads to the formation of new FeIV=O species with relatively intense electronic absorption features in the near-UV region. The presence of these near-UV features allowed us to make the first observation of Fe=O vibrations of S = 1 mononuclear nonheme oxoiron(IV) complexes by resonance Raman spectroscopy. We have also demonstrated that the reactivity of nonheme oxoiron(IV) intermediates is markedly influenced by the axial ligands.

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, P.H.S.

MeSH terms

  • Iron / chemistry*
  • Ligands
  • Organometallic Compounds / chemistry*
  • Oxygen / chemistry*
  • Spectrophotometry, Ultraviolet / methods
  • Spectrum Analysis, Raman / methods*
  • Vibration

Substances

  • Ligands
  • Organometallic Compounds
  • Iron
  • Oxygen