The difference one ligand atom makes – An altered oxygen transfer reaction mechanism caused by an exchange of selenium for sulfur
| Autor: | Xiaoli Ma, Carola Schulzke, Carlos Enrique Abad Andrade, Wolfram Meyer-Klaucke |
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| Rok vydání: | 2010 |
| Předmět: |
Reaction mechanism
Exafs spectroscopy 010405 organic chemistry Inorganic chemistry Substrate (chemistry) chemistry.chemical_element 010402 general chemistry 01 natural sciences Sulfur 0104 chemical sciences Catalysis Inorganic Chemistry chemistry.chemical_compound Crystallography Thioether chemistry Molybdenum Materials Chemistry Physical and Theoretical Chemistry Selenium |
| Zdroj: | Polyhedron. 29:664-668 |
| ISSN: | 0277-5387 |
| DOI: | 10.1016/j.poly.2009.10.018 |
| Popis: | 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)3S(CH2)3O−) 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. |
| Databáze: | OpenAIRE |
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