A heterometallic (Fe6Na8) cage-like silsesquioxane: Synthesis, structure, spin glass behavior and high catalytic activity

The exotic "Asian Lantern" heterometallic cage silsesquioxane [(PhSiO1.5)20(FeO1.5)6(NaO0.5)8(n-BuOH)9.6(C7H8)] (I) was obtained and characterized by X-ray diffraction, EXAFS, topological analyses and DFT calculation. The magnetic property investigations revealed that it shows an unusual spin glass-like behavior induced by a particular triangular arrangement of Fe(iii) ions. Cyclohexane and other alkanes as well as benzene can be oxidized to the corresponding alkyl hydroperoxides and phenol, respectively, by hydrogen peroxide in air in the presence of catalytic amounts of complex I and nitric acid. The I-catalyzed reaction of cyclohexane, c-C6H12, with H216O2 in an atmosphere of 18O2 gave a mixture of labeled and non-labeled cyclohexyl hydroperoxides, c-C6H11-16O-16OH and c-C6H11-18O-18OH, respectively, with an 18O incorporation level of ca. 12%. Compound I also revealed high efficiency in the oxidative amidation of alcohols into amides: in the presence of complex I, only 500 ppm of iron was allowed to reach TON and TOF values of 1660 and 92 h-1. © The Royal Society of Chemistry 2016.

Bilyachenko A.N. 1, 2 , Levitsky M.M.1 , Yalymov A.I.1 , Korlyukov A.A.1, 3 , Vologzhanina A.V.1 , Kozlov Y.N.4, 5 , Shul'Pina L.S.1 , Nesterov D.S.6 , Pombeiro A.J.L.6 , Lamaty F.7 , Bantreil X.7 , Fetre A.7 , Liu D.7 , Martinez J.7 , Long J.8 , Larionova J.8 , Guari Y.8 , Trigub A.L.9 , Zubavichus Y.V.9 , Golub I.E.1 , Filippov O.A.1 , Shubina E.S.1 , Shul'Pin G.B.4, 5
Number of issue
  • 1 Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Str., 28, Moscow, 119991, Russian Federation
  • 2 People's Friendship University of Russia, Miklukho-Maklay Str. 6, Moscow, 117198, Russian Federation
  • 3 Pirogov Russian National Research Medical University, Ostrovitianov str. 1, Moscow, 117997, Russian Federation
  • 4 Semenov Institute of Chemical Physics, Russian Academy of Sciences, ul. Kosygina, dom 4, Moscow, 119991, Russian Federation
  • 5 Plekhanov Russian University of Economics, Stremyannyi pereulok, dom 36, Moscow, 117997, Russian Federation
  • 6 Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Avenida Rovisco Pais, Lisboa, 1049-001, Portugal
  • 7 Institut des Biomolécules Max Mousseron (IBMM), UMR 5247, CNRS, Université de Montpellier, ENSCM Site Triolet, Place Eugène Bataillon, Montpellier, Cedex 5, 34095, France
  • 8 ICGM-UMR5253-Equipe IMNO, Université de Montpellier, Place Eugène Bataillon-CC 1502, Montpellier, Cedex 5, 34095, France
  • 9 National Research Center, Kurchatov Institute, pl. Akad. Kurchatova, dom 1, Moscow, 123098, Russian Federation
Catalyst activity; Cyclohexane; Glass; Metallic compounds; Spin glass; X ray diffraction; Catalytic amounts; Catalyzed reactions; DFT calculation; Oxidative amidation; Spin-glass behavior; Spin-glass-like behaviors; Topological analysis; Triangular arrangements; Iron compounds
Date of creation
Date of change
Short link

Other records

Bilyachenko A.N., Levitsky M.M., Yalymov A.I., Korlyukov A.A., Vologzhanina A.V., Kozlov Y.N., Shul'Pina L.S., Nesterov D.S., Pombeiro A.J.L., Lamaty F., Bantreil X., Fetre A., Liu D., Martinez J., Long J., Larionova J., Guari Y., Trigub A.L., Zubavichus Y.V., Golub I.E., Filippov O.A., Shubina E.S., Shul'Pin G.B.
RSC Advances. Vol. 6. 2016.
Vasvuk Yu.A., Ivanova S.V., Shkolnike L., Kotovskaya Yu.V., Mityaginv A., Oleynikovv E., Orlovaya A., Sumin A.N., Baranov A.A., Boytsov S.A., Galyavich A.S., Kobalavazh D., Kozhevnikova O.V., Konradi A.O., Lopatinyu M., Mareev V.Yu., Novikova D.S., Oganovr G., Rogozaa N., Rotar O.P., Sergatskaya N.V., Skibitsky V.V.
Cardiovascular Therapy and Prevention (Russian Federation). Vserossiiskoe Obshchestvo Kardiologov. Vol. 15. 2016. P. 4-19