DFT and experimental study of nitrosyl carboxylate palladium clusters Pd4(NO)2(RCO2)6 as catalysts for aerobic oxidation of alcoholsстатья
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Дата последнего поиска статьи во внешних источниках: 29 октября 2018 г.
Аннотация:Possible activation pathways for palladium nitrosyl carboxylate complexes Pd4(μ-NO)2(μ-RCO2)6 in reaction of catalytic aerobic oxidation of alcohols are reported. The study was carried out using scalar-relativistic DFT calculations for the system palladium nitrosyl acetate (R = CH3) + methanol. Exchange-correlation functional PBE was found to be the best choice in terms of accuracy and time for calculations. The main pathway includes dissociation of starting 4-nuclear molecule into binuclear species Pd2(NO) (CH3CO2)3, where nitrosyl group keeps bridging coordination mode. Experimental studies showed that palladium nitrosyl acetate (R = CH3) and nitrosyl pivalate (R = CMe3) are moderately active catalysts for aerobic oxidation of benzylic alcohol, (E)-2-hexen-1-ol, (−)-menthol, trans-1,3-diphenyl-2-propen-1-ol and dodecanol-1. The addition of pyridine substantially improved the catalysts performance.