[Fe-S] clusters are ubiquitous electron transfer (ET) cofactors that play an integral role in several enzymes that catalyze multi-e�/H+ redox events. It has been shown that certain clusters can also undergo proton-coupled electron transfer (PCET), though both the mechanism and generality of this type of reaction at biological [Fe-S] clusters remains unknown. This presentation will focus on synthetic [Fe-S] cluster models that undergo PCET. The clusters investigated range from bis-benzimidazolate ligated [2Fe-2S] Rieske cluster mimics to all S-ligated [4Fe-4S] clusters. The various cluster congeners -- oxidized and reduced; deprotonated and protonated -- will first be described, as well as the thermochemistry of their interconversions. Cluster reactivity towards H-atom acceptor/donors will then be discussed, as well as kinetic studies on these reactions. Finally, the thermochemistry and PCET reactivity of the synthetic clusters will be compared to their biological counterparts.

Proton-coupled electron transfer reactions of synthetic [Fe-S] clusters

244th National Meeting (2012)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.