Synthesis and Characterization of Nickel Compounds with Tetradentate Thiolate–Thioether Ligands as Precursors for [NiFe]–Hydrogenase Models. Issue 1 (19th November 2013)

• Record Type: Journal Article
• Authors: Weber, Katharina; Heise, Ingeborg; Weyhermüller, Thomas; Lubitz, Wolfgang
• Is Part Of: European journal of inorganic chemistry. Issue 1(2014)
• Page Start: 148
• Page End: 155
• Publication Date: 2013-11-19
• Subjects: Nickel -- S ligands -- Ligand design -- Transition metals -- Protein models; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201301223
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract: Synthesis and X‐ray structural analyses of three NiS4 compounds with aliphatic tetradentate thiolato/thioether ligands―[Ni(xch)], [Ni(pdtch)], and [Ni(pdtdm)], in which H2 xch, H2 pdtch, and H2 pdtdm 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. Abstract : Three nickel complexes containing chelating S4 ligands were prepared as precursors for [NiFe]–hydrogenase models. Molecular and electronic structures of these compounds are discussed in comparison to the NiS4 site of the enzyme.