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. Author manuscript; available in PMC: 2017 Aug 24.
Published in final edited form as: J Am Chem Soc. 2017 Aug 10;139(33):11434–11442. doi: 10.1021/jacs.7b03966

Scheme 2.

Scheme 2

Adding negative charges such as DNA in the proximity of the [Fe4S4] cluster destabilizes the S 3p orbital energy and increases the S 3p character (α2) in Ψ*. This increase in the Fe-S covalency stabilizes the oxidized more than the reduced state of the cluster and decreases the reduction potential.