Catalytic Reduction of Hydrazine to Ammonia by a Mononuclear Iron(II) Complex on a Tris(thiolato)phosphine Platform

To provide the mechanistic information of nitrogenase at a molecular level, much effort has been made to develop synthetic metal complexes that have enzyme-like reactivity. Herein we obtain an iron­(II) complex binding with a tris­(thiolato)­phosphine ligand, [P­(Ph)4]­[Fe­(PS3″)­(CH3CN)] [1; PS3″ = P­(C6H3-3-Me3Si-2-S)33–] that catalyzes the reduction of hydrazine, an intermediate and a substrate of nitrogenase. The substrate- and product-bound adducts, [N­(Bu)4]­[Fe­(PS3″)­(N2H4)] (2) and [N­(Et)4]­[Fe­(PS3″)­(NH3)] (3), respectively, are also synthesized. This work provides the feasibility that the late stage of biological nitrogen fixation can be conducted at a single iron site with a sulfur-rich ligation environment.