Fe₃S₂ cluster complexes containing aminodiphosphine ligand: synthesis, characterization, crystal structures and electrochemical properties

ABSTRACT

In this article, six new Fe₃S₂ cluster complexes Fe₃(µ₃S)₂(CO)₇[(Ph₂P)₂NR] (1-6) (R = (CH₂)₂CH₃, CH(CH₃)₂, (CH₂)₃CH₃, CH₂CH(CH₃)₂, p-C₆H₄CCH and m-C₆H₄CCH) were successfully synthesized by reactions of Fe₃S₂(CO)₉ and the corresponding aminodiphosphines under refluxing toluene. Meanwhile, treatment of Fe₃S₂(CO)₉ and (Ph₂P)₂NCH(CH₃)Ph afforded two new Fe₃S₂ cluster complexes Fe₃(µ₃-S)₂(CO)₇[(Ph₂P)₂NCH(CH₃)Ph] (7) and Fe₃(µ₃-S)₂(CO)₇[(κ²-Ph₂P)₂NCH(CH₃)(Ph)] (8). Complexes 1–8 were characterized by elemental analysis, FT-IR, NMR spectroscopy, and especially X-ray crystallography. The elctrochemical properties were investigated by cyclic voltammetry, showing that they all have electrocatalytic ability for the reduction of protons to H₂.

GRAPHICAL ABSTRACT

KEYWORDS:

• Fe₃S₂ cluster
• synthesis
• aminodiphosphine
• crystal structure
• electrochemistry

Disclosure statement

No potential conflict of interest was reported by the author(s).

Supporting Information

Additional crystallographic, spectroscopic data, and IR, NMR (¹H, ³¹P) spectra for complexes 1–8 may be found online in the Supporting Information section at the end of the article. CCDC 1982351, 1982322, 1982321, 1982319, 1982316 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: [phone].

Additional information

Funding

This work was supported by Science & Technology Department of Sichuan Province (2020066), Chemical Synthesis and Pollution Control Key Laboratory of Sichuan Province (CSPC201904), Vanadium and Titanium Resource Comprehensive Utilization Key Laboratory of Sichuan Province (2021FTSZ07), Sichuan University of Science & Engineering (2019RC41, CX2021055).