Keggin-Type Heteropoly Salts as Bifunctional Catalysts in Aerobic Baeyer-Villiger Oxidation

Materials
Katarzyna PaminEwa M Serwicka

Abstract

The cobalt, manganese, and iron salts of tungstophosphoric or molybdophosphoric acid with growing content of metals were applied for the first time as catalysts in the Baeyer-Villiger (BV) oxidation of cyclohexanone to ε-caprolactone with molecular oxygen. The catalysts were characterized with Fourier transform infrared spectroscopy (FTIR), X-ray fluorescence (XRF), and ethanol decomposition reaction. Introduction of transition metals into the heteropoly structure increases the activity of resulting heteropoly salts in comparison with parent heteropolyacids. It was shown that the most active catalysts are salts of the heteropoly salts with one metal atom introduced and one proton left (HMPX) type, (where M = Co, Fe, Mn, and X = W, Mo) with the metal to proton ratio equal one. Among all of the studied catalysts, the highest catalytic activity was observed for HCoPW. The effect indicates that both the acidic and redox properties are required to achieve the best performance. The Baeyer-Villiger (BV) oxidation mechanism proposed identifies the participation of heteropoly compounds in three steps of the investigated reaction: oxidation of aldehyde to peracid (redox function), activation of carbonyl group (Lewis acidity), and decompo...Continue Reading

References

Sep 3, 1975·Journal of the American Chemical Society·C J WeschlerF Basolo
Sep 9, 2004·Chemical Reviews·G-J ten BrinkR A Sheldon
Oct 12, 2010·Chembiochem : a European Journal of Chemical Biology·Gonzalo de GonzaloMarco W Fraaije
May 6, 2011·Chemical Reviews·Hannes LeischPeter C K Lau
May 18, 1998·Angewandte Chemie·Giorgio Strukul

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