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Molecules 2016, 21(5), 665; doi:10.3390/molecules21050665

Novel Cage-Like Hexanuclear Nickel(II) Silsesquioxane. Synthesis, Structure, and Catalytic Activity in Oxidations with Peroxides

1
Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Str. 28, 119991 Moscow, Russia
2
Inorganic Chemistry Department, People’s Friendship University of Russia, Miklukho-Maklay Str. 6, 117198 Moscow, Russia
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, 117997 Moscow, Russia
5
Semenov Institute of Chemical Physics, Russian Academy of Sciences, ul. Kosygina, dom 4, 119991 Moscow, Russia
6
Chair of Chemistry and Physics, Plekhanov Russian University of Economics, Stremyannyi pereulok, dom 36, 117997 Moscow, Russia
*
Authors to whom correspondence should be addressed.
Academic Editor: Maxim L. Kuznetsov
Received: 12 April 2016 / Revised: 28 April 2016 / Accepted: 13 May 2016 / Published: 19 May 2016
(This article belongs to the Special Issue Metal Mediated Activation of Small Molecules)
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Abstract

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. View Full-Text
Keywords: metal silsesquioxane; X-ray analysis; topological analysis; oxidation; alkanes; alcohols; meta-chloroperoxybenzoic acid (MCPBA) metal silsesquioxane; X-ray analysis; topological analysis; oxidation; alkanes; alcohols; meta-chloroperoxybenzoic acid (MCPBA)
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

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Bilyachenko, A.N.; Yalymov, A.I.; Shul’pina, L.S.; Mandelli, D.; Korlyukov, A.A.; Vologzhanina, A.V.; Es’kova, M.A.; Shubina, E.S.; Levitsky, M.M.; Shul’pin, G.B. Novel Cage-Like Hexanuclear Nickel(II) Silsesquioxane. Synthesis, Structure, and Catalytic Activity in Oxidations with Peroxides. Molecules 2016, 21, 665.

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