Biomimetic di- or multimetallic complexes featuring N_xH_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_xH_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.

中文翻译：

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硫醇盐桥接的钌-钼配合物，具有末端氮化物和桥接酰胺配体，源自肼的 N-H 和 N-N 键断裂

_{在富硫配位层中以 N x} H _y物种为特征的仿生二金属或多金属配合物在模拟固氮酶生物固氮的可能情景方面引起了相当大的关注。虽然固氮酶的活性位点是一个复杂的异金属硫簇，但 N _x H _{y的可行性}几乎没有研究不同金属位点上的物种。在此，我们报告了一种前所未有的硫醇盐桥接钌-钼络合物，其特征在于通过裂解肼的 N-N 和 N-H 键获得桥接氨基和末端氮化物配体。值得注意的是，这种 RuMo 配合物还能够催化肼还原为氨。总体而言，硫醇盐桥联的 RuMo 平台上这种罕见的肼活化模式为固氮酶中的异金属协同性提供了新的见解。