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.