Theoretical Mechanistic Insights into Dinitrogen Activation by a Diniobium Tetrahydride: Two-State Reactivity and the Role of Potassium Cation Promoter

A “two-state reactivity” scenario has been computationally disclosed for dinitrogen activation by a diniobium tetrahydride. Remarkably, it is revealed that alkali metal cations play a crucial role via alkali···N coordination interaction, which is capable of decreasing the activation barriers of N–H formation and subsequent H₂ elimination in particular. Furthermore, the effect of various alkali metal cations has also been investigated systematically.