期刊
POLYHEDRON
卷 29, 期 1, 页码 664-668出版社
PERGAMON-ELSEVIER SCIENCE LTD
DOI: 10.1016/j.poly.2009.10.018
关键词
Metalloenzymes; Molybdenum; Ligand effects; EXAFS spectroscopy; Catalysis
资金
- DFG (Deutsche Forschungsgemeinschaft)
- DAAD (Deutscher Akademischer Austausch Dienst)
The influence Of Sulfur versus selenium coordination to molybdenum on the oxo transfer reaction mechanisms of functional models for oxidoreductases has been studied. The Solution structure of the dimeric molybdenum compound with tridentate bis-anionic ligands containing a thioether function (O-(CH2)(3)S(CH2)(3)O-) has been determined using EXAFS spectroscopy to be able to compare a feature Of its Solution Structure to that of its selenoether analogue. A significant difference is found for the solution structures of the two compounds. The thioether group remains coordinated in solution, whereas the selenoether does not. The influence of this difference on the catalytic oxo transfer has been investigated in detail by following the catalytic transition of PPh3 to OPPh3 with DMSO as oxygen donor with variation of both substrate concentrations. (C) 2009 Elsevier Ltd. All rights reserved.
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