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Probing Hydrogen Bonding Interactions to Iron-Oxido/Hydroxido Units by 57 Fe Nuclear Resonance Vibrational Spectroscopy.

Andrew C WeitzEthan A HillVictoria F OswaldEmile L BominaarAndrew S BorovikMichael P HendrichYisong Guo
Published in: Angewandte Chemie (International ed. in English) (2018)
Hydrogen bonds (H-bonds) have been shown to modulate the chemical reactivities of iron centers in iron-containing dioxygen-activating enzymes and model complexes. However, few examples are available that investigate how systematic changes in intramolecular H-bonds within the secondary coordination sphere influence specific properties of iron intermediates, such as iron-oxido/hydroxido species. Here, we used 57 Fe nuclear resonance vibrational spectroscopy (NRVS) to probe the Fe-O/OH vibrations in a series of FeIII -hydroxido and FeIV/III -oxido complexes with varying H-bonding networks but having similar trigonal bipyramidal primary coordination spheres. The data show that even subtle changes in the H-bonds to the Fe-O/OH units result in significant changes in their vibrational frequencies, thus demonstrating the utility of NRVS in studying the effect of the secondary coordination sphere to the reactivities of iron complexes.
Keyphrases
  • energy transfer
  • iron deficiency
  • molecular dynamics simulations
  • high resolution
  • quantum dots
  • signaling pathway
  • mass spectrometry
  • raman spectroscopy
  • living cells
  • genetic diversity
  • aqueous solution
  • visible light