Abstract
AbstractSynthesis and X‐ray structural analyses of three NiS4 compounds with aliphatic tetradentate thiolato/thioether ligands―[Ni(xch)], [Ni(pdtch)], and [Ni(pdtdm)], in which H2xch, H2pdtch, and H2pdtdm are α,α′‐bis(trans‐2‐mercapto‐1‐thiacyclohexyl)‐o‐xylene, 1,3‐bis(trans‐2‐mercapto‐1‐thiacyclohexyl)propane, and 1,9‐dimercapto‐3,7‐dithia‐2,2,8,8‐tetramethylnonane―are reported and further investigated by NMR spectroscopy, electronic absorption spectroscopy, and cyclic voltammetry. The molecular and electronic structures of these nickel complexes are described. All complexes are square planar and show only a small tetrahedral distortion, consistent with a low‐spin nickel(II) center (S = 0). Cyclic voltammetry data reveal that for all compounds both one‐electron oxidation and reduction are irreversible, which is explained by means of DFT calculations. The presented complexes are discussed with regard to their suitability as precursors for dinuclear [NiFe]–hydrogenase model compounds.
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