Ammonia Formation Catalyzed by a Dinitrogen-Bridged Dirhenium Complex Bearing PNP-Pincer Ligands under Mild Reaction Conditions**

A series of rhenium complexes bearing a pyridine-based PNP-type pincer ligand are synthesized from rhenium phosphine complexes as precursors. A dinitrogen-bridged dirhenium complex bearing the PNP-type pincer ligands catalytically converts dinitrogen into ammonia during the reaction with KC₈ as a reductant and [HPCy₃]BAr^F₄ (Cy=cyclohexyl, Ar^F=3,5-(CF₃)₂C₆H₃) as a proton source at −78 °C to afford 8.4 equiv of ammonia based on the rhenium atom of the catalyst. The rhenium-dinitrogen complex also catalyzes silylation of dinitrogen in the reaction with KC₈ as a reductant and Me₃SiCl as a silylating reagent under ambient reaction conditions to afford 11.7 equiv of tris(trimethylsilyl)amine based on the rhenium atom of the catalyst. These results demonstrate the first successful example of catalytic nitrogen fixation under mild reaction conditions using rhenium-dinitrogen complexes as catalysts.