Si10Cu6N4 Cage Hexacoppersilsesquioxanes Containing N Ligands: Synthesis, Structure, and High Catalytic Activity in Peroxide Oxidations

The synthesis, composition, and catalytic properties of a new family of hexanuclear Cu(II)-based phenylsilsesquioxanes are described here. Structural studies of 17 synthesized compounds revealed the general principle underlying their molecular topology: viz., a central metal oxide layer consisting of two Cu3 trimers is coordinated by two cyclic [PhSiO1.5]5 siloxanolate ligands to form a skewed sandwich architecture with the composition [(PhSiO1.5)10(CuO)6]2+. In addition to this O ligation by the siloxanolate rings, two opposite copper ions are additionally coordinated by the nitrogen atoms of corresponding N ligand(s), such as 2,2′-bipyridine (compounds 1-9), 1,10-phenanthroline (compounds 10-13), mixed 1,10-phenanthroline/2,2′-bipyridine (compound 14), or bathophenanthroline (compounds 15-17). Finally, the charge balance is maintained by two HO- (compounds 1-7, 10-13, and 15-17), two H3CO- (compound 8), or two CH3COO- (compounds 9 and 14) anions. Complexes 1 and 10 exhibited a high activity in the oxidative amidation oxidation of alcohols. Compounds 1, 10, and 15 are very efficient homogeneous catalysts in the oxidation of alkanes and alcohols with peroxides. © 2017 American Chemical Society.

Kulakova A.N. 1, 2 , Bilyachenko A.N. 1, 2 , Levitsky M.M.1 , Khrustalev V.N. 2 , Korlyukov A.A.1, 3 , Zubavichus Y.V.4 , Dorovatovskii P.V.4 , Lamaty F.5 , Bantreil X.5 , Villemejeanne B.5 , Martinez J.5 , Shul'Pina L.S.1 , Shubina E.S.1 , Gutsul E.I.1 , Mikhailov I.A.6 , Ikonnikov N.S.1 , Tsareva U.S.1 , Shul'Pin G.B.6, 7
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  • 1 Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Str., 28, Moscow, Russian Federation
  • 2 Peoples' Friendship University of Russia (RUDN University), Miklukho-Maklay Str., 6, Moscow, Russian Federation
  • 3 Pirogov Russian National Research Medical University, Ostrovitianov str., 1, Moscow, Russian Federation
  • 4 National Research Center, Kurchatov Institute, Akademika Kurchatova pl., 1, Moscow, Russian Federation
  • 5 Institut des Biomolécules Max Mousseron (IBMM), UMR 5247, CNRS, Université de Montpellier, ENSCM, Site Triolet, Place Eugène Bataillon, Montpellier Cedex 5, 34095, France
  • 6 Plekhanov Russian University of Economics, Stremyannyi pereulok, dom 36, Moscow, Russian Federation
  • 7 Semenov Institute of Chemical Physics, Russian Academy of Sciences, ulitsa Kosygina, dom 4, Moscow, Russian Federation
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