Tridentate N2S ligand from 2,2′-dithiodibenzaldehyde and N,N-dimethylethylenediamine: Synthesis, structure, and characterization of a Ni(II) complex with relevance to Ni Superoxide Dismutase

Nickel Superoxide Dismutase (NiSOD) and the A-cluster of Carbon Monoxide Dehydrogenase/Acetyl Coenzyme A Synthase (CODH/ACS) both feature active sites with Ni coordinated by thiolate and amide donors. It is likely that the particular set of donors is important in tuning the redox potential of the Ni center(s). We report herein an expansion of our efforts involving the use of 2,2′-dithiodibenzaldehyde (DTDB) as a synthon for metal–thiolate complexes to reactions with Ni complexes of N,N-dimethylethylenediamine (dmen). In the presence of coordinating counterions, these reactions result in monomeric square-planar complexes of the tridentate N2S donor ligand derived from the Schiff-base condensation of dmen and DTDB. In the absence of a coordinating counterion, we have isolated a Ni(II) complex with an asymmetric N2S2 donor set involving one amine and one imine N donor in addition to two thiolate donors. This latter complex is discussed with respect to its relevance to the active site of NiSOD.

Reacting 2,2′-dithiodibenzaldehyde with Ni(II) complexes of N,N-dimethylethylenediamine produces, in the presence of coordinating counterions, complexes of a tridentate N2S donor ligand and, in the absence thereof, a complex with N2S2 donor set (amine, imine, two thiolate donors),which is discussed with respect to relevance to the active site of Ni Superoxide Dismutase.Figure optionsDownload as PowerPoint slideHighlights
► Ni complexes of mixed N/S donor ligands.
► Four coordinate mononuclear complexes with N2SX coordination sphere.
► One complex with amine, imine, and two thiolate donors.
► Relevance to active site of Ni Superoxide Dismutase.