High Catalytic Activity of Heterometallic (Fe6Na7 and Fe6Na6) Cage Silsesquioxanes in Oxidations with Peroxides
AbstractTwo types of heterometallic (Fe(III),Na) silsesquioxanes—[Ph5Si5O10]2[Ph10Si10O21]Fe6(O2‒)2Na7(H3O+)(MeOH)2(MeCN)22.214.171.124(MeCN), I, and [Ph5Si5O10]2[Ph4Si4O8]2Fe6Na6(O2‒)3(MeCN)8.5(H2O)8.44, II—were obtained and characterized. X-ray studies established distinctive structures of both products, with pair of Fe(III)-O-based triangles surrounded by siloxanolate ligands, giving fascinating cage architectures. Complex II proved to be catalytically active in the formation of amides from alcohols and amines, and thus becoming a rare example of metallasilsesquioxanes performing homogeneous catalysis. Benzene, cyclohexane, and other alkanes, as well as alcohols, can be oxidized in acetonitrile solution to phenol—the corresponding alkyl hydroperoxides and ketones, respectively—by hydrogen peroxide in air in the presence of catalytic amounts of complex II and trifluoroacetic acid. Thus, the cyclohexane oxidation at 20 °C gave oxygenates in very high yield of alkanes (48% based on alkane). The kinetic behaviour of the system indicates that the mechanism includes the formation of hydroxyl radicals generated from hydrogen peroxide in its interaction with di-iron species. The latter are formed via monomerization of starting hexairon complex with further dimerization of the monomers. View Full-Text
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Yalymov, A.I.; Bilyachenko, A.N.; Levitsky, M.M.; Korlyukov, A.A.; Khrustalev, V.N.; Shul’pina, L.S.; Dorovatovskii, P.V.; Es’kova, M.A.; Lamaty, F.; Bantreil, X.; Villemejeanne, B.; Martinez, J.; Shubina, E.S.; Kozlov, Y.N.; Shul’pin, G.B. High Catalytic Activity of Heterometallic (Fe6Na7 and Fe6Na6) Cage Silsesquioxanes in Oxidations with Peroxides. Catalysts 2017, 7, 101.
Yalymov AI, Bilyachenko AN, Levitsky MM, Korlyukov AA, Khrustalev VN, Shul’pina LS, Dorovatovskii PV, Es’kova MA, Lamaty F, Bantreil X, Villemejeanne B, Martinez J, Shubina ES, Kozlov YN, Shul’pin GB. High Catalytic Activity of Heterometallic (Fe6Na7 and Fe6Na6) Cage Silsesquioxanes in Oxidations with Peroxides. Catalysts. 2017; 7(4):101.Chicago/Turabian Style
Yalymov, Alexey I.; Bilyachenko, Alexey N.; Levitsky, Mikhail M.; Korlyukov, Alexander A.; Khrustalev, Victor N.; Shul’pina, Lidia S.; Dorovatovskii, Pavel V.; Es’kova, Marina A.; Lamaty, Frédéric; Bantreil, Xavier; Villemejeanne, Benoît; Martinez, Jean; Shubina, Elena S.; Kozlov, Yuriy N.; Shul’pin, Georgiy B. 2017. "High Catalytic Activity of Heterometallic (Fe6Na7 and Fe6Na6) Cage Silsesquioxanes in Oxidations with Peroxides." Catalysts 7, no. 4: 101.
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