期刊
CATALYSIS SCIENCE & TECHNOLOGY
卷 5, 期 1, 页码 595-610出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c4cy00864b
关键词
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资金
- Department of Science and Technology, New Delhi, India
- University Grants Commission, Basic Science Research Fellowship, New Delhi, India
An efficient and eco-compatible route for the selective oxidation of a variety of thioethers to the corresponding sulfoxide or sulfone with 30% aqueous H2O2 in water, using newly synthesized peroxoniobium (pNb) complexes as catalysts, is described. The catalysts with formulas Na-2[Nb(O-2)(3)(arg)]center dot 2H(2)O (arg = arginate) (NbA) and Na-2[Nb(O-2)(3)(nic)(H2O)]center dot H2O (nic = nicotinate) (NbN) have been synthesized from the reaction of sodium tetraperoxoniobate with 30% H2O2 and the respective organic ligand in an aqueous medium, and these have been comprehensively characterized by elemental analysis, spectral studies (FTIR, Raman, H-1 NMR, C-13 NMR and UV-vis), EDX analysis and TGA-DTG analysis. The density functional theory (DFT) method has been used to investigate the structure of the synthesized pNb complexes. The catalysts are physiologically safe and can be reused for at least six reaction cycles without losing their activity or selectivity. The oxidation is chemoselective for sulfides or sulfoxides leaving the C=C or alcoholic moiety unaffected. The developed methodologies, apart from being high yielding and straightforward, are completely free from halogen, organic co-solvent, or co-catalysts.
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