Citation: Xufeng LIU, Shaojie WANG, Peihua ZHAO. Ligand substitution of diiron hexacarbonyl complex with aminodiphosphine to prepare diiron aminophosphine complexes relevant to [FeFe]-hydrogenases[J]. Chinese Journal of Inorganic Chemistry, ;2025, 41(9): 1851-1858. doi: 10.11862/CJIC.20250131 shu

Ligand substitution of diiron hexacarbonyl complex with aminodiphosphine to prepare diiron aminophosphine complexes relevant to [FeFe]-hydrogenases

1.
School of Materials and Chemical Engineering, Ningbo University of Technology, Ningbo, Zhejiang 315211, China
2.
School of Materials Science and Engineering, North University of China, Taiyuan 030051, China

Corresponding author: Peihua ZHAO, zph2004@nuc.edu.cn
Received Date: 16 April 2025
Revised Date: 16 June 2025

Figures(4)

To extend a new family of aminophosphine-coordinated [FeFe]-hydrogenase mimics for catalytic hydrogen (H₂) evolution, we carried out the ligand substitutions of diiron hexacarbonyl precursors [Fe₂(μ-X₂pdt)(CO)₆] (X₂pdt=(SCH₂)₂CX₂, X=Me, H) with aminodiphosphines (Ph₂PCH₂)₂NY(Y=(CH₂)₂OH, (CH₂)₃OH) to obtain two new diiron aminophosphine complexes [Fe₂(L1)(μ-Me₂pdt)(CO)₅] (1) and [Fe₂(L2)(μ-H₂pdt)(CO)₅] (2), where L1=3-[(diphenylphosphaneyl)methyl]oxazolidine, L2=3-[(diphenylphosphaneyl)methyl]-1, 3-oxazinane. Moreover, the structures of 1 and 2 have been fully confirmed by elemental analysis, spectroscopic techniques, and single-crystal X-ray diffraction. Using cyclic voltammetry (CV), we investigated the electrochemical redox performance and proton reduction activities of 1 and 2 in acetic acid (HOAc). The CV study indicates that diiron aminophosphine complexes 1 and 2 can be considered to be hydrogenase-inspired diiron molecular electrocatalysts for the reduction of protons into H₂ generation in the presence of HOAc.
- [FeFe]-hydrogenases,
- diiron model complexes,
- aminophosphine ligand,
- structure,
- electrochemical performance
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