Synthesis and Characterization of Biomimetic Asymmetric Iron Thiolate Complexes Containing Ferrocene Units Related to the Active Site of [FeFe]-hydrogenase

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Using the strong electron-donor ligand PMe3 to replicate the function of ligand CN- in the enzyme, and the redox-active ligand PPh2Fc to replicate the function of [4Fe4S] ferredoxin-like-cluster. The synthesis, electrochemical characterization, NMR spectroscopy and X-ray single crystallography of a series of asymmetric diiron carbonyl dithiolate complexes, [(m-xdt)Fe2(CO)4(PMe3)(PPh2Fc)] ; xdt = edt (1), pdt (2), NH-adt (3), NnPr-adt (4) and NBn-adt (5) had been done in this work. The oxidation reactions of 1 and 3 by three different oxidants, FcBArF24, [(4-Br-C6H4)3N][BF4] and [(4-Br-C6H4)3N][SbCl6], were monitored by FT-IR. The Cl- adduct species ((m-CO)[1-Cl]+ and (m-Cl)[3]+) can be observed when using the oxidant [(4-Br-C6H4)3N][SbCl6] and were confirmed by Mass spectra and designed experiments.