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Iron-sulfur clusters: why iron?

Kasper P Jensen1

  • 1Department of Theoretical Chemistry, Lund University, Chemical Centre, P.O. Box 124, S-221 00, Lund, Sweden. kasper.jensen@yale.edu

Journal of Inorganic Biochemistry
|May 24, 2006
PubMed
Summary
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Iron is uniquely suited for iron-sulfur clusters due to its low inner-sphere reorganization energy, facilitating efficient electron transfer. This property explains iron

Area of Science:

  • Biochemistry
  • Inorganic Chemistry
  • Computational Chemistry

Background:

  • Iron-sulfur clusters are crucial metalloproteins involved in various biological redox reactions.
  • The specific role of iron as the metal center in these clusters remains an area of interest.

Purpose of the Study:

  • To investigate the fundamental reasons behind iron's prevalence in iron-sulfur clusters.
  • To compare the electronic properties of iron with other transition metals in cluster models.

Main Methods:

  • Density functional calculations were employed to model electron transfer processes.
  • Inner-sphere reorganization energies were computed for iron and other metal ions (Mn, Co, Ni, Cu).

Main Results:

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  • Iron exhibits significantly lower inner-sphere reorganization energies (21 kJ/mol for 1Fe, 46 kJ/mol for 2Fe) compared to other metals.
  • Other metal ions showed higher reorganization energies, ranging from 57-135 kJ/mol (1Fe) and 94-140 kJ/mol (2Fe).
  • These findings were consistent for both 1Fe and 2Fe cluster models.

    • Conclusions:

    • A low inner-sphere reorganization energy is a key factor favoring iron in iron-sulfur clusters.
    • This property is linked to the stability of occupied anti-bonding orbitals during redox reactions.
    • Iron's electronic structure makes it an optimal metal for efficient electron transfer in these biological systems.