Although alkyl complexes of [Fe4S4] clusters have been invoked as intermediates in a
number of enzymatic reactions, obtaining a detailed understanding of their reactivity patterns
and electronic structures has been difficult owing to their transient nature. To address this
challenge, we herein report the synthesis and characterization of a 3: 1 site-differentiated
[Fe4S4] 2+–alkyl cluster. Whereas [Fe4S4] 2+ clusters typically exhibit pairwise delocalized
electronic structures in which each Fe has a formal valence of 2.5+, Mössbauer …

Although alkyl complexes of [Fe₄S₄] clusters have been invoked as intermediates in a
number of enzymatic reactions, obtaining a detailed understanding of their reactivity patterns
and electronic structures has been difficult owing to their transient nature. To address this
challenge, we herein report the synthesis and characterization of a 3: 1 site-differentiated
[Fe₄S₄] ²⁺-alkyl cluster. Whereas [Fe₄S₄] ²⁺ clusters typically exhibit pairwise
delocalized electronic structures in which each Fe has a formal valence of 2.5+, Mössbauer …