New phosphorous-based [FeFe]-hydrogenase models

[FeFe]-hydrogenases have attracted research for more than twenty years as paragons for the design of new catalysts for the hydrogen evolution reaction (HER). The bridging dithiolate comprising a secondary amine as bridgehead is the key element for the reactivity of native [FeFe]-hydrogenases and was therefore the midpoint of hundreds of biomimetic hydrogenase models. However, within those mimics, phosphorous is barely seen as a central element in the azadithiolato bridge despite being the direct heavier homologue of nitrogen. We herein synthesized three new phosphorous based [FeFe]-hydrogenase models by reacting dithiols \((HSCH_{2})_{2}P(O)R\) (R = Me, OEt, OPh) with \(Fe_{3}(CO)_{12}\). All synthesized mimics show catalytic reactivity regarding HER and change their mechanisms depending on the strength of the used acid. In all presented mimics, the oxide is the center of reactivity, independent of the nature of the bridgehead. However, the phosphorous atom might be reduced by the methods we present herein to alter the reactivity of the model compounds towards protons and oxygen