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Iron-sulfur clusters: the road to room temperature
Brighton A Skeel1, Daniel L M Suess2
1Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA, USA.
Iron-sulfur (Fe-S) clusters are vital for metabolism, with unique electronic structures enabling diverse reactions. Understanding their excited states is crucial for explaining Fe-S cluster reactivity under physiological conditions.
Area of Science:
- Biochemistry
- Bioinorganic Chemistry
- Protein Science
Background:
- Iron-sulfur (Fe-S) clusters are essential cofactors in numerous metabolic enzymes across all domains of life.
- Their unique electronic structures, distinct from mononuclear iron enzymes, dictate their diverse catalytic functions.
- Understanding the electronic basis of Fe-S cluster reactivity is critical for comprehending biological processes.
Purpose of the Study:
- To summarize the key electronic structure features that confer uniqueness to Fe-S clusters.
- To emphasize the necessity of studying Fe-S cluster electronic properties under physiological conditions.
- To highlight the role of thermally populated excited states in Fe-S cluster reactivity.
Main Methods:
- Review and synthesis of existing literature on Fe-S cluster electronic structures.
- Discussion of theoretical and experimental studies characterizing low-energy excited states.
- Analysis of the consensus model for Fe-S cluster excited state manifolds and bonding.
Main Results:
- Fe-S clusters possess rich electronic structures that differ significantly from mononuclear iron centers.
- At ambient temperatures, both ground and numerous excited electronic states are populated, influencing reactivity.
- A consensus model for the low-energy excited states and their associated bonding interactions has been established.
Conclusions:
- A comprehensive understanding of Fe-S cluster reactivity requires consideration of excited electronic states.
- The electronic properties and reactivity patterns of these excited states are crucial under physiological conditions.
- There may be uncharacterized functional roles for alternate spin states and valence configurations in Fe-S clusters of varying nuclearities.
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