The compds. of this study served as structural and functional biomimetics of the [FeFe]-Hydrogenase active site and have demonstrated a redox level-dependent structural rearrangement that is unique in dinuclear organometallic chem. The distinctive "rotated", as contrasted to sym. butterfly, structure is the epicenter of the natural, base metal, hydrogen-producing catalysts. The installation of bridgehead bulk in the -SCH2CR2CH2S- dithiolate (R = Me, Et) model complexes produces 6-membered FeS2C3 cyclohexane-type rings that in the boat c...
