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Related Experiment Videos

A novel diiron complex as a functional model for hemerythrin.

H Arii1, S Nagatomo, T Kitagawa

  • 1Department of Applied Chemistry, Faculty of Engineering, Nagoya Institute of Technology, Japan.

Journal of Inorganic Biochemistry
|January 2, 2001
PubMed
Summary
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This study synthesized diiron(II) complexes as hemerythrin models. Reversible dioxygen binding was observed, suggesting a peroxo anion coordination, influenced by the binding environment's hydrophobicity.

Area of Science:

  • Bioinorganic Chemistry
  • Coordination Chemistry
  • Biomimetic Chemistry

Background:

  • Hemerythrin is an iron-containing protein that transports oxygen.
  • Functional models of hemerythrin are crucial for understanding its oxygen-binding mechanism.
  • Novel dinucleating polypyridine ligands can create biomimetic iron complexes.

Purpose of the Study:

  • To synthesize and characterize novel diiron(II) complexes using a new ligand (HTPPDO) as functional models of hemerythrin.
  • To investigate the dioxygen-binding properties of these diiron complexes.
  • To elucidate the coordination mode of dioxygen and the factors influencing binding reversibility.

Main Methods:

  • Synthesis of diiron(II) complexes with N,N,N',N'-tetrakis(6-pivalamido-2-pyridylmethyl)-1,3-diaminopropan-2-ol (HTPPDO).

Related Experiment Videos

  • Structural characterization using X-ray diffraction, electronic absorption, IR spectroscopy, and electrochemistry.
  • Dioxygen-binding studies employing electronic absorption, resonance Raman, and ESR spectroscopies.

    • Main Results:

    • Crystal structures revealed asymmetric and symmetric coordination of iron centers with HTPPDO and bridging ligands.
    • Reversible dioxygen binding was observed for complexes 1 and 2, indicated by a characteristic LMCT band and peroxo anion coordination (mu-1,2 mode).
    • Complex 3 showed irreversible dioxygen binding, suggesting the hydrophobicity of the binding environment is key, not iron redox potentials.

    Conclusions:

    • The synthesized diiron(II) complexes serve as effective functional models of hemerythrin.
    • Dioxygen binds as a peroxo anion in a mu-1,2 fashion to the diiron core.
    • The reversibility of dioxygen binding is primarily dictated by the hydrophobicity of the active site.