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Spectroscopic and electrochemical comparison of [FeFe]-hydrogenase active-site inspired compounds: Diiron monobenzenethiolate compounds containing electron-donating and withdrawing groups

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Abstract The novel compounds [Fe2(μ-SC6H4-p-NO2)2(CO)6] (1), [Fe2(μ-SC6H4-p-tBu)(μ-SC6H4-p-NO2)(CO)6] (2), [Fe2(μ-SC6H4-p-tBu)2(CO)6] (3), [Fe2(μ-SC6H4-p-tBu)(μ-SC6H4-p-CF3)(CO)6] (4) and [Fe2(μ-SC6H4-p-OCH3)(μ-SC6H4-p-CF3)(CO)6] (5) have been characterized by 1H-NMR, FTIR, elemental analysis, and cyclic voltammetry. X-ray crystallography of compounds… Click to show full abstract

Abstract The novel compounds [Fe2(μ-SC6H4-p-NO2)2(CO)6] (1), [Fe2(μ-SC6H4-p-tBu)(μ-SC6H4-p-NO2)(CO)6] (2), [Fe2(μ-SC6H4-p-tBu)2(CO)6] (3), [Fe2(μ-SC6H4-p-tBu)(μ-SC6H4-p-CF3)(CO)6] (4) and [Fe2(μ-SC6H4-p-OCH3)(μ-SC6H4-p-CF3)(CO)6] (5) have been characterized by 1H-NMR, FTIR, elemental analysis, and cyclic voltammetry. X-ray crystallography of compounds 1 and 2 reveal an anti (ax,eq) S-aryl ligand orientation in the solid state. Carbonyl IR spectra and reduction potentials correlate strongly with Hammett constants of the electron donating/withdrawing groups. Evaluation for electrocatalytic formation of dihydrogen from acetic acid indicates a low overpotential of activity of 0.26 V for compound 5.

Keywords: sc6h4; withdrawing groups; donating withdrawing; fe2 sc6h4; electron donating

Journal Title: Polyhedron
Year Published: 2021

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