Diiron dichalcogenolato complexes of the form Fe2(�-SeCH2(CH2)nCH2Se-�)(CO)6 have been prepared and the catalytic activities of these complexes have been studied by electrochemical and computational methods. The electrochemical reversibility and the electrocatalytic production of H2 from AcOH were found to improve as the length of diselenolato bridge linker increased. This is attributed to formation of a stabilized bridging CO �rotated� structure in the anions as shown below, consistent with the hypothesis that this structure is critical to H2 production in [FeFe]-hydrogenases.

Effects of increasing the diselenolato bridge linker chain length in dichalcogenolato [FeFe]-hydrogenase model compounds

245th National Meeting (2013)

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