A Bioinspired Iron-Molybdenum μ-Nitrido Complex and Its Reactivity toward Ammonia Formation.
Linan SuDawei YangYang JiangYahui LiKai DiBaomin WangShengfa YeJingping QuPublished in: Angewandte Chemie (International ed. in English) (2022)
Multimetallic nitride species, especially those containing biologically related iron or molybdenum, are fundamentally important to understand the nitrogen reduction process catalysed by FeMo-nitrogenase. However, until now, there remains no report about the construction of structurally well-defined FeMo heteronuclear nitrido complex and its reactivity toward ammonia formation. Herein, a novel thiolate-bridged Fe II Mo VI complex featuring a bent Fe-N≡Mo fragment is synthesized and structurally characterized, which can be easily protonated to form a μ-imido complex. Subsequently, through the proton-coupled electron transfer (PCET) process, this imido species can smoothly convert into the μ-amido complex, which can further undergo reductive protonation to afford the FeMo complex containing an ammine ligand. Overall, we present the first well-defined {Fe(μ-S) 2 Mo} platform that can give a panoramic picture for the late stage (N 3- →NH 2- →NH 2 - →NH 3 ) of biological nitrogen reduction by the heterometallic cooperativity.