Unusual Tri-, Hexa-, and Nonanuclear Cu(II) Cage Methylsilsesquioxanes: Synthesis, Structures, and Catalytic Activity in Oxidations with Peroxides

Three types of unusual cagelike copper(II) methylsilsesquioxanes, namely, nona- [(MeSiO1.5)18(CuO)9] 1, hexa- [(MeSiO1.5)10(HO0.5)2(CuO)6(C12H8N2)2(MeSiO1.5)10(HO0.5)1.33(CH3COO0.5)0.67(CuO)6(C12H8N2)2] 2, [(MeSiO1.5)10(CuO)6(MeO0.5)2(C10H8N2)2] 3, and trinuclear [(MeSiO1.5)8(CuO)3(C10H8N2)2] 4, were obtained in 44%, 27%, 20%, and 16% yields, respectively. Nuclearity and structural fashion of products was controlled by the choice of solvent system and ligand, specifically assisting the assembling of cage. Structures of 1-4 were determined by single-crystal X-ray diffraction analysis. Compounds 1 and 4 are the first cage metallasilsesquioxanes, containing nine and three Cu ions, respectively. Product 1 is the first observation of nonanuclear metallasilsesquioxane ever. Unique architecture of 4 represents early unknown type of molecular geometry, based on two condensed pentamembered siloxane cycles. Topological analysis of metal clusters in products 1-4 is provided. Complex 1 efficiently catalyzes oxidation of alcohols with tert-butylhydroperoxide TBHP to ketones or alkanes with H2O2 to alkyl hydroperoxides in acetonitrile. © 2017 American Chemical Society.

Authors
Bilyachenko A.N. 1, 2 , Kulakova A.N. 1, 2 , Levitsky M.M.1 , Petrov A.A. 1 , Korlyukov A.A.1, 3 , Shul’pina L.S.1 , Khrustalev V.N. 1, 2 , Dorovatovskii P.V.4 , Vologzhanina A.V.1 , Tsareva U.S.1 , Golub I.E. 1, 2 , Gulyaeva E.S.1 , Shubina E.S.1 , Shul’pin G.B.5, 6
Number of issue
7
Language
English
Pages
4093-4103
Status
Published
Volume
56
Year
2017
Organizations
  • 1 Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Str., 28, Moscow, 119991, Russian Federation
  • 2 People’s Friendship University of Russia, Miklukho-Maklay Str., 6, Moscow, 117198, Russian Federation
  • 3 Pirogov Russian National Research Medical University, Ostrovitianov str., 1, Moscow, 117997, Russian Federation
  • 4 National Research Center “Kurchatov Institute”, Akademika Kurchatova pl., 1, Moscow, 123182, Russian Federation
  • 5 Semenov Institute of Chemical Physics, Russian Academy of Sciences, ulitsa Kosygina, dom 4, Moscow, 119991, Russian Federation
  • 6 Plekhanov Russian University of Economics, Stremyannyi pereulok, dom 36, Moscow, 117997, Russian Federation
Date of creation
19.10.2018
Date of change
19.10.2018
Short link
https://repository.rudn.ru/en/records/article/record/5550/
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