S K- and Mo L-edge X-ray absorption spectroscopy to determine metal-ligand charge distribution in molybdenum-sulfur compounds.
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.
Rompel
A
A
Physical Biosciences Division, Lawrence Berkeley National Laboratory,CA 94720-5230, USA. rompela@nwz.uni-muenster.de
Cinco
R M
RM
Robblee
J H
JH
Latimer
M J
MJ
McFarlane
K L
KL
Huang
J
J
Walters
M A
MA
Yachandra
V K
VK
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*
D008024:Ligands; D009942:Organometallic Compounds; D013457:Sulfur Compounds; D008982:Molybdenum