Catalytic Borylation of Dinitrogen into Borylamines and Borylhydrazines Using Rhenium Complexes under Ambient Reaction Conditions

In the presence of a catalytic amount of a dinitrogen-bridged dirhenium complex bearing PNP-type pincer ligands, an atmospheric pressure of dinitrogen reacted with potassium as a reductant and dicyclohexylchloroborane as a borylating reagent at room temperature to give 14.4 equiv of ammonia and 3.2 equiv of hydrazine based on the rhenium atom of the catalyst upon hydrolysis (20.8 equiv of fixed N atom). This result demonstrates the first successful example of the borylation of dinitrogen into ammonia and hydrazine equivalents under ambient conditions with rhenium complexes as catalysts.