Citation: Linjie ZHU, Xufeng LIU. 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. doi: 10.11862/CJIC.20240416 shu

Synthesis, characterization and electrocatalytic hydrogen evolution of two di-iron complexes containing a phosphine ligand with a pendant amine

Linjie ZHU ,
Xufeng LIU ^,

School of Materials and Chemical Engineering, Ningbo University of Technology, Ningbo, Zhejiang 315211, China

Corresponding author: Xufeng LIU, nkxfliu@126.com
Received Date: 22 November 2024
Revised Date: 27 February 2025

Figures(7)

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(κ^2-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.
- [FeFe]-hydrogenases,
- diphosphine,
- crystal structure,
- electrocatalytic hydrogen evolution
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