title: Electronic structure of transition metal-cysteine complexes from X-ray absorption spectroscopy.
abstract: The electronic structures of HgII, NiII, CrIII, and MoV complexes with cysteine were investigated by sulfur K-edge X-ray absorption near-edge structure (XANES) spectroscopy and density functional theory. The covalency in the metal-sulfur bond was determined by analyzing the intensities of the electric-dipole allowed pre-edge features appearing in the XANES spectra below the ionization threshold. Because of the well-defined structures of the selected cysteine complexes, the current work provides a reference set for further sulfur K-edge XAS studies of bioinorganic active sites with transition metal-sulfur bonds from cysteine residues as well as more complex coordination compounds with thiolate ligands.
authors: Department of Chemistry, University of Calgary, Calgary, Alberta, T2N 1N4, Canada.
authors: Bonnie O
authors: BO
authors: Leung
authors: Farideh
authors: F
authors: Jalilehvand
authors: Robert K
authors: RK
authors: Szilagyi
mesh_terms: D002857:Chromium / Q000737:chemistry*; D003198:Computer Simulation; D003545:Cysteine / Q000737:chemistry*; D004583:Electrons; D008024:Ligands; D008628:Mercury / Q000737:chemistry*; D008956:Models, Chemical; D008982:Molybdenum / Q000737:chemistry*; D009532:Nickel / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D013057:Spectrum Analysis / Q000379:methods; D013438:Sulfhydryl Compounds / Q000737:chemistry; D014965:X-Rays
chemical_list: D008024:Ligands; D009942:Organometallic Compounds; D013438:Sulfhydryl Compounds; D002857:Chromium; D009532:Nickel; D008982:Molybdenum; D008628:Mercury; D003545:Cysteine