title: S K- and Mo L-edge X-ray absorption spectroscopy to determine metal-ligand charge distribution in molybdenum-sulfur compounds.
abstract: Mo L-edge and S K-edge X-ray absorption spectroscopy were applied to investigate the charge distribution between Mo and S in a series of Mo thiolate compounds, which serve as amide-sulfur H-bonding models and exhibit different redox potentials arising from polar group effects and ligand hydrogen bonds near the redox center. For all oxidized complexes, the S K-edge spectra exhibit a thiolate-based pre-edge feature centered at 2470.2 eV and the inflection point oCCurs at 2472.0 eV. No intense pre-edge feature is observed in the spectra for the reduced Mo model compounds and the energy shift of the S K-edge position depends on the S-ligand. Correlations between ligand charge density and the redox potential of the Mo-S cores are observed.
authors.affiliation: Physical Biosciences Division, Lawrence Berkeley National Laboratory,CA 94720-5230, USA. rompela@nwz.uni-muenster.de
authors.forename: A
authors.initials: A
authors.lastname: Rompel
authors.forename: R M
authors.initials: RM
authors.lastname: Cinco
authors.forename: J H
authors.initials: JH
authors.lastname: Robblee
authors.forename: M J
authors.initials: MJ
authors.lastname: Latimer
authors.forename: K L
authors.initials: KL
authors.lastname: McFarlane
authors.forename: J
authors.initials: J
authors.lastname: Huang
authors.forename: M A
authors.initials: MA
authors.lastname: Walters
authors.forename: V K
authors.initials: VK
authors.lastname: Yachandra
mesh_terms: D008024:Ligands; D008982:Molybdenum / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D013052:Spectrometry, X-Ray Emission / Q000379:methods; D013457:Sulfur Compounds / Q000737:chemistry*
chemical_list: D008024:Ligands; D009942:Organometallic Compounds; D013457:Sulfur Compounds; D008982:Molybdenum