FeFe]‐hydrogenase H‐cluster mimics mediated by mixed (S, Se) and (S, Te) bridging moieties: Insight into molecular structures and electrochemical characteristics

Abstract

AbstractTwo synthetic models of the active site of [FeFe]‐hydrogenase containing mixed (S, Se) and (S, Te) bridges have been synthesized and characterized. These complexes [Fe2(CO)6{μ‐S(CH2)4E‐μ)}] (E = Se (1), Te (2)) are obtained in moderate yields from the reaction of Fe3(CO)12 with 1,2‐thiaselenane or 1,2‐thiatellurane. They have been characterized by spectroscopic techniques (IR, 1H‐, 13C{1H}‐, 77Se{1H}‐, 125Te{1H}‐NMR, and MS) and elemental analysis. The structures of [Fe2(CO)6{μ‐S(CH2)4Se‐μ)}] and [Fe2(CO)6{μ‐S(CH2)4Te‐μ)}] are determined by X‐ray structure determination and show the expected butterfly geometry. Moreover, the influence of the mixed chalcogen atoms on the redox properties and the catalytic behavior of 1 and 2 are studied using cyclic voltammetry.