Spectral and structural insights of copper reduction pathways in the system of CuX2-R2S (X=Cl, Br; R=allyl, n-propyl)
| Autor: | Błażej Dziuk, Volodymyr Olijnyk |
|---|---|
| Rok vydání: | 2021 |
| Předmět: |
Thioether oxidation
010405 organic chemistry Chemistry Organic Chemistry chemistry.chemical_element Sulfoxide Crystal structure 010402 general chemistry 01 natural sciences Copper Redox 0104 chemical sciences Analytical Chemistry Inorganic Chemistry Crystallography chemistry.chemical_compound Copper(II) halide Halogen X-ray crystallography UV-Vis spectroscopy titration Acetonitrile Single crystal Spectroscopy |
| Zdroj: | Journal of Molecular Structure. 1225:129113 |
| ISSN: | 0022-2860 |
| Popis: | We have explored the behaviour of Cu(II)/Cu(I) redox couple in the system CuX2-R2S, X = Cl, Br; R = allyl, n-propyl, under anhydrous and anaerobic conditions, thus simulating the reduction half cycle in the copper catalyzed oxidation of thioethers. In doing so, the Cl−Br substitution was critical for tuning the reduction potentials, while the replacement of propyl group by allyl group supported the trapping of oxidation by-product, halogen molecules. It was therefore possible to use the spectrophotometric titration, thereby providing information on the distribution of complex species in acetonitrile solution. The study showed that the trinuclear mixed−valence copper (I-II-II) aggregates play a crucial role in the evolution of the redox process. The crystal structures of mixed-valence phase, [CuICuII2Cl5(dipropylsulfide)2], as well as full-reduced Cu(I) species, [Cu5Br5(dipropylsulfide)3], have been also determined by single crystal X-ray diffraction. The first one is considered as one of crystallographic “snapshots” of an intermediate involved in sulfoxide formation, while the latter represents the end product built from porous chiral networks. |
| Databáze: | OpenAIRE |
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