Steric Switching from Photochemical to Thermal Reaction Pathways for Enhanced Efficiency in Metal-Mediated Nitrogen Fixation

Programmed manipulation of the subtle interplay of nonbonded steric interactions within a supporting ligand environment has been used for the conversion of a photochemically driven chemical cycle for group 6 metal-mediated nitrogen fixation into a thermally promoted process with increased energy efficiency and atom economy for key transformations involving NN bond cleavage and N-atom functionalization of coordinated N<sub>2</sub>.