The role of bridging ligands in dinitrogen reduction and functionalization by uranium multimetallic complexes

Cooperativity between metal centres is identified as a crucial step in dinitrogen reduction both for the industrial Haber-Bosch process and for the natural fixation of nitrogen by nitrogenase enzymes, but the mechanism of N₂ reduction remains poorly understood. This is in large part because multimetallic complexes that reduce and functionalize dinitrogen in the absence of strong alkali reducing agents are crucial to establish a structure-activity relationship, but remain extremely rare. Recently, we reported a multimetallic nitride-bridged diuranium(III) complex capable of reducing and functionalizing dinitrogen. Here we show that an analogous complex assembled with an oxo instead of a nitride linker also effects the four-electron reduction of dinitrogen, but the reactivity of the resulting oxo-(N₂) complex differs significantly from that of the nitride-(N₂). Computational studies show a different bonding scheme for the dinitrogen where the bridging nitride does participate in the binding and consequent activation of N₂, while the oxide does not.