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.