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| Synthesis, characterization and electrocatalytic hydrogen evolution of two di-iron complexes containing a phosphine ligand with a pendant amine |
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| Abstract: To explore new biomimics for the [FeFe]-hydrogenases active site, two di-iron complexes containing a phosphine ligand with a pendant amine were synthesized and characterized. Reaction of complex [Fe2(CO)6(μ-pdt)] (1), where pdt=SCH2CH2CH2S, with a diphosphine ligand (Ph2PCH2)2NC10H15 (dppad) and Me3NO·2H2O gave a major product [Fe2(CO)5(mpad)(μ-pdt)] (2) in 60% yield together with a minor product [Fe2(CO)4(κ2-dppad)(μ-pdt)] (3) in 6% yield, where mpad=Ph2PCH2NHC10H15. Complexes 2 and 3 were identified by elemental analysis, IR, 1H NMR, 31P NMR, and single-crystal X-ray diffraction analysis. The crystal structure of complex 2 contains an apicallycoordinated phosphine ligand mpad whereas complex 3·0.5CH2Cl2 contains a chelated diphosphine ligand dppad in an apical-basal position. The Fe-Fe bond length in complex 2 [0.251 66(6) nm] is notably shorter than that in complex 3·0.5CH2Cl2 [0.255 88(6) nm]. Furthermore, the electrochemical properties of complexes 2 and 3 were investigated by cyclic voltammetry (CV), revealing that their CV curves contained two reduction peaks and one oxidation peak within the solvent window. The electrocatalytic properties of both complexes showed that they can catalyze the reduction of protons to H2 with HOAc as a proton source. For comparison, the catalytic efficiency (turnover frequency) of 3 was slightly better than that of 2. |
| Keywords: [FeFe]-hydrogenases diphosphine crystal structure electrocatalytic hydrogen evolution |
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| ZHU Linjie,LIU Xufeng.Synthesis, characterization and electrocatalytic hydrogen evolution of two di-iron complexes containing a phosphine ligand with a pendant amine[J].Chinese Journal of Inorganic Chemistry,2025,41(5):939-947. |
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