Abstract or Keywords
X-ray crystallographic structure of [Fe2(µ-3,6-dichloro-1,2-benzenedithiolato)(CO)5Sb(O)Ph3] above the linear voltammetric response obtained for [Fe2(µ-3,6-dichloro-1,2-benzenedithiolato)(CO)5L] when L = CO (blue), L = Sb(O)Ph3 (purple), L = AsPh3 (green) and L = PPh3 (red).
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•Synthesis and characterization of novel pnictogen containing organometallic compounds.•Electrochemical comparison of pnictogen iron-sulfur dithiolates.•Hydrogen-generation from weak acid sources.•Bio-inspired electrocatalysts.•Hypervalent antimony.
The effect of replacing one CO ligand of the competent proton reduction electrocatalyst [(μ-Cl2-bdt)Fe2(CO)6] (“Cl2-bdt” = 3,6-dichloro-1,2-benzenedithiolato), A, with a pnictogen-based ligand has been explored. Four novel compounds have been synthesized and characterized, including X-ray crystallographic structures: [Fe2(µ-Cl2-bdt)(CO)5PPh3] (1), [Fe2(µ-Cl2-bdt)(CO)5AsPh3] (2), [Fe2(µ-Cl2-bdt)(CO)5Sb(O)PPh3] (3), and [Fe2(µ-Cl2-bdt)(CO)4(SbPPh3)2] (4). Notably, 3 represents an uncommon hypervalent antimony 12-Sb-5 compound. The three mono-pnictogen compounds (1–3) were produced in yields of 44–58% and have been investigated electrochemically. Evaluation for electrocatalytic formation of dihydrogen in the presence of acetic acid for compounds 1–3 shows negligible advantage over compound A.