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

Alexey N Bilyachenko; Alexey I Yalymov; Lidia S Shul'pina; Dalmo Mandelli; Alexander A Korlyukov; Anna V Vologzhanina; Marina A Es'kova; Elena S Shubina; Mikhail M Levitsky; Georgiy B Shul'pin

doi:10.3390/molecules21050665

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

Molecules. 2016 May 19;21(5):665. doi: 10.3390/molecules21050665.

Authors

Affiliations

¹ Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Str. 28, 119991 Moscow, Russia. bilyachenko@ineos.ac.ru.
² Inorganic Chemistry Department, People's Friendship University of Russia, Miklukho-Maklay Str. 6, 117198 Moscow, Russia. bilyachenko@ineos.ac.ru.
³ Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Str. 28, 119991 Moscow, Russia. alexyalymov@gmail.com.
⁴ Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Str. 28, 119991 Moscow, Russia. shulpina@ineos.ac.ru.
⁵ Center of Natural and Human Sciences, Federal University of ABC (UFABC), Santa Adélia Street, 166, Bangu, Santo André, SP 09210-170, Brazil. dalmo.mandelli@ufabc.edu.br.
⁶ Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Str. 28, 119991 Moscow, Russia. alex@xrlab.ineos.ac.ru.
⁷ Chemistry Department, Russian National Research Medical University, Ostrovitianov str. 1, 117997 Moscow, Russia. alex@xrlab.ineos.ac.ru.
⁸ Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Str. 28, 119991 Moscow, Russia. vologzhanina@mail.ru.
⁹ Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Str. 28, 119991 Moscow, Russia. marinaeskovskaya@gmail.com.
¹⁰ Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Str. 28, 119991 Moscow, Russia. shu@ineos.ac.ru.
¹¹ Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Str. 28, 119991 Moscow, Russia. levitsk@ineos.ac.ru.
¹² Semenov Institute of Chemical Physics, Russian Academy of Sciences, ul. Kosygina, dom 4, 119991 Moscow, Russia. shulpin@chph.ras.ru.
¹³ Chair of Chemistry and Physics, Plekhanov Russian University of Economics, Stremyannyi pereulok, dom 36, 117997 Moscow, Russia. shulpin@chph.ras.ru.

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.

Keywords: X-ray analysis; alcohols; alkanes; meta-chloroperoxybenzoic acid (MCPBA); metal silsesquioxane; oxidation; topological analysis.

MeSH terms

Catalysis
Nickel / chemistry*
Organosilicon Compounds / chemistry*
Oxidation-Reduction
Peroxides / chemistry*

Substances

1,3-bis(1,1,3,3,5,5-hexaethoxy-1,3,5-trisilacyclohexyl)propane
Organosilicon Compounds
Peroxides
Nickel