A thiolate-bridged ruthenium-molybdenum complex featuring terminal nitrido and bridging amido ligands derived from the N-H and N-N bond cleavage of hydrazine.

Biomimetic di- or multimetallic complexes featuring N x H y species in a sulfur-rich coordination sphere have attracted considerable attention in modelling the possible scenarios of biological nitrogen fixation by nitrogenases. Although the active site of nitrogenases is a complex heterometallic sulfur cluster, the feasibility of N x H y species on different metal sites is scarcely investigated. Herein, we report an unprecedented thiolate-bridged ruthenium-molybdenum complex featuring bridging amido and terminal nitrido ligands obtained by cleaving the N-N and N-H bonds of hydrazine. Remarkably, this RuMo complex is also capable of catalyzing the reduction of hydrazine to ammonia. Overall, this rare activation pattern of hydrazine on a thiolate-bridged RuMo platform provides new insight into the heterometallic cooperativity in nitrogenase.