title: Toward functional Ni-SOD biomimetics: achieving a structural/electronic correlation with redox dynamics.
abstract: We have prepared and characterized a Ni complex with an N(3)S(2) ligand set (1) that represents the first isolable synthetic model of the reduced form of the Ni-SOD (SOD = superoxide dismutase) active site featuring all relevant donor functionality in the proper spatial distribution. As revealed by X-ray crystallography, the axial py-N donor of 1 does not bind Ni(II) in the solid state or in solution like SOD. Oxidation of 1 provides a disulfide-linked dinuclear species, [{Ni(N(3)S(2))}(2)] (2), which we have isolated and characterized. Moreover, the 1 → 2 conversion is reversible, much like redox cycling in the enzyme.
authors: Department of Chemistry and Center for Computational Chemistry, The University of Georgia, 1001 Cedar Street, Athens, Georgia 30602, United States.
authors: Eric M
authors: EM
authors: Gale
authors: Andrew C
authors: AC
authors: Simmonett
authors: Joshua
authors: J
authors: Telser
authors: Henry F
authors: HF
authors: Schaefer
authors: Todd C
authors: TC
authors: Harrop
mesh_terms: D040761:Biomimetic Materials / Q000138:chemical synthesis / Q000737:chemistry*; D020134:Catalytic Domain; D018360:Crystallography, X-Ray; D004563:Electrochemistry; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D056004:Molecular Dynamics Simulation; D009532:Nickel / Q000737:chemistry*; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D010084:Oxidation-Reduction; D021241:Spectrometry, Mass, Electrospray Ionization; D013056:Spectrophotometry, Ultraviolet; D013482:Superoxide Dismutase / Q000737:chemistry*
chemical_list: D009942:Organometallic Compounds; D009532:Nickel; D013482:Superoxide Dismutase