Since the discovery of the iron-only Hydrogenase enzyme's Fe2S2 active site component, various molecular catalysts containing iron and sulfur in a butterfly structure have been synthesized to create a viable H2-producing system. We seek to design an electrocatalyst in which a diiron metallocenter has the appropriate electronic properties, to mimic the enzyme's catalytic behavior.   We have synthesized �-dithiol-Fe2(CO)6-n(L)n catalysts to investigate how variations in electronic, steric, and atomic structure impact electrocatalytic activity for the reduction of protons. Systematic changes to the Fe2S2 coordination sphere have been made: incremental increase of methyl substituents on the sulfur bridge; incremental increase of chlorination on an aromatic sulfur bridge; carbonyl replacement with s-donor ligands.Spectroscopic, computational and electrolysis data illustrate catalytic trends upon structural manipulation of the catalyst (when homogenously present with a proton source). Electroanalytical results include desirable anodic shifts in reduction potential, rate of catalysis enhancement, and mechanistic insight into catalysis.

Structural manipulation of Fe<sub>2</sub>S<sub>2</sub> hydrogenase-inspired electrocatalysts: How can we achieve the enzyme's fascinating catalytic properties?

244th National Meeting (2012)

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Structural manipulation of Fe2S2 hydrogenase-inspired electrocatalysts: How can we achieve the enzyme's fascinating catalytic properties?

Structural manipulation of Fe₂S₂ hydrogenase-inspired electrocatalysts: How can we achieve the enzyme's fascinating catalytic properties?