Three N-substituted selenium-bridged diiron complexes [{(μ-SeCH2)2NC6H4R}Fe2(CO)6] (R = 4-NO2, 7; R = H, 8; R = 4-CH3, 9) were firstly prepared as biomimetic models for the Fe–Fe hydrogenases active site. Models 7–9 could be generated by the convergent reaction of [(μ-HSe)2Fe2(CO)6] (6) with N,N-bis(hydroxymethyl)-4-nitroaniline (1), N,N-bis(hydroxymethyl)aniline (2), and N,N-bis(hydroxymethyl)-4-methylaniline (3) in 46–52% yields. All the new complexes 7–9 were characterized by IR, 1H and 13C NMR and HRMS spectra and their molecular structures were determined by single-crystal X-ray analysis. The redox properties of 7–9 and their dithiolate analogues [{(μ-SCH2)2NC6H4R}Fe2(CO)6] (R = 4-NO2, 7s; R = H, 8s; R = 4-CH3, 9s) were evaluated by cyclic voltammograms. The electrochemical proton reduction by 9 and 9s were investigated in the presence of p-toluenesulfonic acid (HOTs) to evaluate the influence of changing the coordinating S atoms of the bridging ligands to Se atoms on the electrocatalytic activity for proton reduction.
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