The Di-Iron Subsite of All-Iron Hydrogenase: Mechanism of Cyanation of a Synthetic {2Fe3S}–Carbonyl Assembly

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Abstract
This paper describes the kinetics and intimate mechanisms associated with cyanation of {2Fe3S} assemblies to give species structurally related to the subsite of all‐iron hydrogenase. Stopped‐flow FTIR spectroscopy has enabled the quantitation of the dynamics of five well‐defined steps that experimentally illustrate the role of bridging carbonyls in the assembly of the dicyanide species, how on–off sulfur ligation can have a dramatic effect on cyanation kinetics and how the {2Fe3S} core stabilises bridging carbonyl species.

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