Proton-Coupled Reduction of an Iron Cyanide Complex to Methane and Ammonia

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Abstract

Nitrogenase enzymes mediate the six-electron reductive cleavage of cyanide to CH4 and NH3. Herein we demonstrate for the first time the liberation of CH4 and NH3 from a well-defined iron cyanide coordination complex, [SiPiPr3]Fe(CN) (where [SiPiPr3] represents a tris(phosphine)silyl ligand), on exposure to proton and electron equivalents. [SiPiPr3]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 CH4 and NH3. Comparative studies with a related [SiPiPr3]Fe(CNMe2) complex suggests the possibility of multiple, competing mechanisms for cyanide activation and reduction.

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