title: Novel Cage-Like Hexanuclear Nickel(II) Silsesquioxane. Synthesis, Structure, and Catalytic Activity in Oxidations with Peroxides.
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.
authors.affiliation: Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Str. 28, 119991 Moscow, Russia. bilyachenko@ineos.ac.ru.|Inorganic Chemistry Department, People's Friendship University of Russia, Miklukho-Maklay Str. 6, 117198 Moscow, Russia. bilyachenko@ineos.ac.ru.
authors.forename: Alexey N
authors.initials: AN
authors.lastname: Bilyachenko
authors.affiliation: Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Str. 28, 119991 Moscow, Russia. alexyalymov@gmail.com.
authors.forename: Alexey I
authors.initials: AI
authors.lastname: Yalymov
authors.affiliation: Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Str. 28, 119991 Moscow, Russia. shulpina@ineos.ac.ru.
authors.forename: Lidia S
authors.initials: LS
authors.lastname: Shul'pina
authors.affiliation: 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.
authors.forename: Dalmo
authors.initials: D
authors.lastname: Mandelli
authors.affiliation: Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Str. 28, 119991 Moscow, Russia. alex@xrlab.ineos.ac.ru.|Chemistry Department, Russian National Research Medical University, Ostrovitianov str. 1, 117997 Moscow, Russia. alex@xrlab.ineos.ac.ru.
authors.forename: Alexander A
authors.initials: AA
authors.lastname: Korlyukov
authors.affiliation: Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Str. 28, 119991 Moscow, Russia. vologzhanina@mail.ru.
authors.forename: Anna V
authors.initials: AV
authors.lastname: Vologzhanina
authors.affiliation: Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Str. 28, 119991 Moscow, Russia. marinaeskovskaya@gmail.com.
authors.forename: Marina A
authors.initials: MA
authors.lastname: Es'kova
authors.affiliation: Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Str. 28, 119991 Moscow, Russia. shu@ineos.ac.ru.
authors.forename: Elena S
authors.initials: ES
authors.lastname: Shubina
authors.affiliation: Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Str. 28, 119991 Moscow, Russia. levitsk@ineos.ac.ru.
authors.forename: Mikhail M
authors.initials: MM
authors.lastname: Levitsky
authors.affiliation: Semenov Institute of Chemical Physics, Russian Academy of Sciences, ul. Kosygina, dom 4, 119991 Moscow, Russia. shulpin@chph.ras.ru.|Chair of Chemistry and Physics, Plekhanov Russian University of Economics, Stremyannyi pereulok, dom 36, 117997 Moscow, Russia. shulpin@chph.ras.ru.
authors.forename: Georgiy B
authors.initials: GB
authors.lastname: Shul'pin
mesh_terms: D002384:Catalysis; D009532:Nickel / Q000737:chemistry*; D017646:Organosilicon Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D010545:Peroxides / Q000737:chemistry*
chemical_list: C512088:1,3-bis(1,1,3,3,5,5-hexaethoxy-1,3,5-trisilacyclohexyl)propane; D017646:Organosilicon Compounds; D010545:Peroxides; D009532:Nickel
keywords: X-ray analysis; alcohols; alkanes; meta-chloroperoxybenzoic acid (MCPBA); metal silsesquioxane; oxidation; topological analysis