Dinitrogen Splitting Coupled to Protonation

The coupling of electron- and proton-transfer steps provides a general concept to control the driving force of redox reactions. N-2 splitting of a molybdenum dinitrogen complex into nitrides coupled to a reaction with Bronsted acid is reported. Remarkably, our spectroscopic, kinetic, and computational mechanistic analysis attributes N-N bond cleavage to protonation in the periphery of an amide pincer ligands rather than the {Mo-N-2-Mo} core. The strong effect on electronic structure and ultimately the thermochemistry and kinetic barrier of N-N bond cleavage is an unusual case of a proton-coupled metal-to-ligand charge transfer process, highlighting the use of proton-responsive ligands for nitrogen fixation.