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Zusammenfassung:
Iron nitrides are key intermediates in biological nitrogen fixation and the industrial Haber–Bosch process, used to form ammonia from dinitrogen. However, the proposed successive conversion of nitride to ammonia remains elusive. In this regard, the search for well-described multi-iron nitrido model complexes and investigations on controlling their reactivity towards ammonia formation have long been of great challenge and importance. Here we report a well-defined thiolate-bridged FeIVFeIV μ-nitrido complex featuring an uncommon bent Fe–N–Fe moiety. Remarkably, this complex shows excellent reactivity toward hydrogenation with H2 at ambient conditions, forming ammonia in high yield. Combined experimental and computational studies demonstrate that a thiolate-bridged FeIIIFeIII μ-amido complex is a key intermediate, which is generated through an unusual two-electron oxidation of H2. Moreover, ammonia production was also realized by treating this diiron μ-nitride with electrons and water as a proton source.
