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.

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
  • 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
Date of change
Short link

Other records

Minasny B., Malone B.P., McBratney A.B., Angers D.A., Arrouays D., Chambers A., Chaplot V., Chen Z.-S., Cheng K., Das B.S., Field D.J., Gimona A., Hedley C.B., Hong S.Y., Mandal B., Marchant B.P., Martin M., McConkey B.G., Mulder V.L., O'Rourke S., Richer-de-Forges A.C., Odeh I., Padarian J., Paustian K., Pan G., Poggio L., Savin I., Stolbovoy V., Stockmann U., Sulaeman Y., Tsui C.-C., Vågen T.-G., Winowiecki L., Van Wesemael B.
Geoderma. Elsevier. Vol. 292. 2017. P. 59-86