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Catalysts 2017, 7(4), 101; doi:10.3390/catal7040101

High Catalytic Activity of Heterometallic (Fe6Na7 and Fe6Na6) Cage Silsesquioxanes in Oxidations with Peroxides

1
A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Str., 28, Moscow 119991, Russia
2
Inorganic Chemistry Department, People’s Friendship University of Russia (RUDN University), Miklukho-Maklay Str., 6, Moscow 117198, Russia
3
Chemistry department, Therapeutic faculty, Pirogov Russian National Research Medical University, Ostrovitianov Str., 1, Moscow 117997, Russia
4
National Research Center “Kurchatov Institute”, Akademika Kurchatova pl., 1, Moscow 123182, Russia
5
Institut des Biomolécules Max Mousseron (IBMM) UMR 5247, CNRS, Université de Montpellier, ENSCM, Université de Montpellier Campus Triolet Place Eugène Bataillon, Montpellier CEDEX 5, 34095, France
6
Semenov Institute of Chemical Physics, Russian Academy of Sciences, Ulitsa Kosygina, dom 4, Moscow 119991, Russia
7
Chair of Chemistry and Physics, Plekhanov Russian University of Economics, Stremyannyi pereulok, dom 36, Moscow 117997, Russia
*
Authors to whom correspondence should be addressed.
Received: 16 February 2017 / Revised: 17 March 2017 / Accepted: 21 March 2017 / Published: 27 March 2017
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Abstract

Two types of heterometallic (Fe(III),Na) silsesquioxanes—[Ph5Si5O10]2[Ph10Si10O21]Fe6(O2‒)2Na7(H3O+)(MeOH)2(MeCN)4.5.1.25(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
Keywords: alkanes; amides; hydrogen peroxide; dinuclear complexes; iron complexes; metallasiloxanes alkanes; amides; hydrogen peroxide; dinuclear complexes; iron complexes; metallasiloxanes
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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.

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