Next Article in Journal
Dicyclopentadiene Hydroformylation to Value-Added Fine Chemicals over Magnetically Separable Fe3O4-Supported Co-Rh Bimetallic Catalysts: Effects of Cobalt Loading
Previous Article in Journal
Caprolactam-Based Brønsted Acidic Ionic Liquids for Biodiesel Production from Jatropha Oil
Open AccessArticle

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

A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Str., 28, Moscow 119991, Russia
Inorganic Chemistry Department, People’s Friendship University of Russia (RUDN University), Miklukho-Maklay Str., 6, Moscow 117198, Russia
Chemistry department, Therapeutic faculty, Pirogov Russian National Research Medical University, Ostrovitianov Str., 1, Moscow 117997, Russia
National Research Center “Kurchatov Institute”, Akademika Kurchatova pl., 1, Moscow 123182, Russia
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
Semenov Institute of Chemical Physics, Russian Academy of Sciences, Ulitsa Kosygina, dom 4, Moscow 119991, Russia
Chair of Chemistry and Physics, Plekhanov Russian University of Economics, Stremyannyi pereulok, dom 36, Moscow 117997, Russia
Authors to whom correspondence should be addressed.
Catalysts 2017, 7(4), 101;
Received: 16 February 2017 / Revised: 17 March 2017 / Accepted: 21 March 2017 / Published: 27 March 2017
Two types of heterometallic (Fe(III),Na) silsesquioxanes—[Ph5Si5O10]2[Ph10Si10O21]Fe6(O2‒)2Na7(H3O+)(MeOH)2(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
Show Figures

Figure 1

MDPI and ACS Style

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.

Show more citation formats Show less citations formats
Note that from the first issue of 2016, MDPI journals use article numbers instead of page numbers. See further details here.

Article Access Map by Country/Region

Search more from Scilit
Back to TopTop