Open AccessS K ‐ and Mo L ‐edge X‐ray absorption spectroscopy to determine metal–ligand charge distribution in molybdenum–sulfur compounds
Author(s) -
Rompel Annette,
Cinco Roehl M.,
Robblee John H.,
Latimer Matthew J.,
McFarlane Karen L.,
Huang Jiong,
Walters Marc A.,
Yachandra Vittal K.
Publication year - 2001
Publication title -
journal of synchrotron radiation
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.172
H-Index - 99
ISSN - 1600-5775
DOI - 10.1107/s0909049500017702
Subject(s) - chemistry , molybdenum , ligand (biochemistry) , crystallography , absorption spectroscopy , charge density , redox , k edge , spectroscopy , spectral line , inorganic chemistry , physics , biochemistry , receptor , quantum mechanics , astronomy
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.