Article ID Journal Published Year Pages File Type
1322889 Journal of Organometallic Chemistry 2013 5 Pages PDF
Abstract

Three variations of the common [FeFe]-Hydrogenase active site mimic μ–(SCH2CH2S)–Fe2(CO)6, 1, have been studied: μ-(SCH(CH3)CH2S)–Fe2(CO)6, 2; μ-(SCH(CH3)CH(CH3)S)–Fe2(CO)6, 3; and μ-(SCH2CH(CH2OH)S)–Fe2(CO)6, 4. The electrochemistry of these four species is compared, indicating that 3 displays greater durability upon electrochemical cycling. This enhanced stability is ascribed to steric blockage of decomposition routes, rather than any change to the Fe2S2 butterfly structure. Electrocatalysis using a weak acid (4-tert-butylphenol, pKa = 27.5 in acetonitrile) is observed for each catalyst with similar overpotential. The enhanced stability of the reduction products of 3 leads to a modest increase of the apparent catalytic rate. Compound 4 was tested for an enhancement of the rate of the acid deprotonation step; compound 4 failed to behave in such a manner, providing no improvement in electrochemical catalysis compared to the parent compound.

Graphical abstractStructures of the four compounds studied above their cyclic voltammetric response.Figure optionsDownload full-size imageDownload as PowerPoint slideHighlights► Electrochemical comparison of iron–sulphur dithiolates. ► Hydrogen-generation from weak acid sources. ► Bio-inspired electrocatalysts.

Related Topics
Physical Sciences and Engineering Chemistry Inorganic Chemistry
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