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Nitrogenase enzymes mediate the six‐electron reductive cleavage of cyanide to CH₄and NH₃. Herein we demonstrate for the first time the liberation of CH₄and NH₃from a well‐defined iron cyanide coordination complex, [SiP^iPr₃]Fe(CN) (where [SiP^iPr₃] represents a tris(phosphine)silyl ligand), on exposure to proton and electron equivalents. [SiP^iPr₃]Fe(CN) additionally serves as a useful entry point to rare examples of terminally‐bound Fe(CNH) and Fe(CNH₂) species that, in accord with preliminary mechanistic studies, are plausible intermediates of the cyanide reductive protonation to generate CH₄and NH₃. Comparative studies with a related [SiP^iPr₃]Fe(CNMe₂) complex suggests the possibility of multiple, competing mechanisms for cyanide activation and reduction.

Given the importance of Fe–NO complexes in both human biology and the global nitrogen cycle, there has been interest in understanding their diverse electronic structures. Herein a redox series of isolable iron nitrosyl complexes stabilized by a tris(phosphine)borane (TPB) ligand is described. These structurally characterized iron nitrosyl complexes reside in the following highly reduced Enemark–Feltham numbers: {FeNO}⁸, {FeNO}⁹, and {FeNO}¹⁰. These {FeNO}^8–10compounds are each low‐spin, and feature linear yet strongly activated nitric oxide ligands. Use of Mössbauer, EPR, NMR, UV/Vis, and IR spectroscopy, in conjunction with DFT calculations, provides insight into the electronic structures of this uncommon redox series of iron nitrosyl complexes. In particular, the data collectively suggest that {TPBFeNO}^8–10are all remarkably covalent. This covalency is likely responsible for the stability of this system across three highly reduced redox states that correlate with unusually high Enemark–Feltham numbers.