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 H2O2to alkyl hydroperoxides in acetonitrile.
Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences , Vavilov Str., 28, 119991 Moscow, Russia.|People's Friendship University of Russia , Miklukho-Maklay Str., 6, 117198 Moscow, Russia.
Alexey N
http://orcid.org/0000-0003-3136-3675
AN
Bilyachenko
Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences , Vavilov Str., 28, 119991 Moscow, Russia.|People's Friendship University of Russia , Miklukho-Maklay Str., 6, 117198 Moscow, Russia.
Alena N
AN
Kulakova
Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences , Vavilov Str., 28, 119991 Moscow, Russia.
Mikhail M
MM
Levitsky
Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences , Vavilov Str., 28, 119991 Moscow, Russia.
Artem A
AA
Petrov
Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences , Vavilov Str., 28, 119991 Moscow, Russia.|Pirogov Russian National Research Medical University , Ostrovitianov str., 1, 117997 Moscow, Russia.
Alexander A
AA
Korlyukov
Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences , Vavilov Str., 28, 119991 Moscow, Russia.
Lidia S
LS
Shul'pina
Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences , Vavilov Str., 28, 119991 Moscow, Russia.|People's Friendship University of Russia , Miklukho-Maklay Str., 6, 117198 Moscow, Russia.
Victor N
http://orcid.org/0000-0001-8806-2975
VN
Khrustalev
National Research Center "Kurchatov Institute" , Akademika Kurchatova pl., 1, 123182 Moscow, Russia.
Pavel V
PV
Dorovatovskii
Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences , Vavilov Str., 28, 119991 Moscow, Russia.
Anna V
http://orcid.org/0000-0002-6228-303X
AV
Vologzhanina
Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences , Vavilov Str., 28, 119991 Moscow, Russia.
Ulyana S
US
Tsareva
Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences , Vavilov Str., 28, 119991 Moscow, Russia.|People's Friendship University of Russia , Miklukho-Maklay Str., 6, 117198 Moscow, Russia.
Igor E
http://orcid.org/0000-0003-4142-454X
IE
Golub
Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences , Vavilov Str., 28, 119991 Moscow, Russia.
Ekaterina S
ES
Gulyaeva
Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences , Vavilov Str., 28, 119991 Moscow, Russia.
Elena S
ES
Shubina
Semenov Institute of Chemical Physics, Russian Academy of Sciences , ulitsa Kosygina, dom 4, Moscow 119991, Russia.|Plekhanov Russian University of Economics , Stremyannyi pereulok, dom 36, Moscow 117997, Russia.
Georgiy B
GB
Shul'pin