Novel cage-like hexanuclear nickel(II) silsesquioxane. Synthesis, structure, and catalytic activity in oxidations with peroxides

New hexanuclear nickel(II) silsesquioxane [(PhSiO1.5)12(NiO)6(NaCl)] (1) was synthesized as its dioxane-benzonitrile-water complex (PhSiO1,5)12(NiO)6(NaCl)(C4H8O2)13(PhCN)2(H2O)2 and studied by X-ray and topological analysis. The compound exhibits cylinder-like type of molecular architecture and represents very rare case of polyhedral complexation of metallasilsesquioxane with benzonitrile. Complex 1 exhibited catalytic activity in activation of such small molecules as light alkanes and alcohols. Namely, oxidation of alcohols with tert-butylhydroperoxide and alkanes with meta-chloroperoxybenzoic acid. The oxidation of methylcyclohexane gave rise to the isomeric ketones and unusual distribution of alcohol isomers. © 2016 by the authors; licensee MDPI.

Authors
Bilyachenko A.N. 1, 2 , Yalymov A.I.1 , Shul'pina L.S.1 , Mandelli D.3 , Korlyukov A.A.1, 4 , Vologzhanina A.V.1 , Es'kova M.A.1 , Shubina E.S.1 , Levitsky M.M.1 , Shul'pin G.B.5, 6
Journal
Molecules
Publisher
MDPI AG
Number of issue
5
Language
English
Status
Published
Link
External link
DOI
10.3390/MOLECULES21050665
Number
665
Volume
21
Year
2016
Organizations
  • 1 Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Str. 28, Moscow, 119991, Russian Federation
  • 2 Inorganic Chemistry Department, People's Friendship University of Russia, Miklukho-Maklay Str. 6, Moscow, 117198, Russian Federation
  • 3 Center of Natural and Human Sciences, Federal University of ABC (UFABC), Santa Adélia Street, 166, Bangu, Santo André, SP 09210-170, Brazil
  • 4 Chemistry Department, Russian National Research Medical University, Ostrovitianov str. 1, Moscow, 117997, Russian Federation
  • 5 Semenov Institute of Chemical Physics, Russian Academy of Sciences, ul. Kosygina, dom 4, Moscow, 119991, Russian Federation
  • 6 Department of Chemistry and Physics, Plekhanov Russian University of Economics, Stremyannyi pereulok, dom 36, Moscow, 117997, Russian Federation
Keywords
Alcohols; Alkanes; meta-chloroperoxybenzoic acid (MCPBA); Metal silsesquioxane; Oxidation; Topological analysis; X-ray analysis
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