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

Alexey N Bilyachenko; Alena N Kulakova; Mikhail M Levitsky; Artem A Petrov; Alexander A Korlyukov; Lidia S Shul'pina; Victor N Khrustalev; Pavel V Dorovatovskii; Anna V Vologzhanina; Ulyana S Tsareva; Igor E Golub; Ekaterina S Gulyaeva; Elena S Shubina; Georgiy B Shul'pin

doi:10.1021/acs.inorgchem.7b00061

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

Inorg Chem. 2017 Apr 3;56(7):4093-4103. doi: 10.1021/acs.inorgchem.7b00061. Epub 2017 Mar 20.

Authors

Alexey N Bilyachenko^{1

2}, Alena N Kulakova^{1

2}, Mikhail M Levitsky¹, Artem A Petrov¹, Alexander A Korlyukov^{1

3}, Lidia S Shul'pina¹, Victor N Khrustalev^{1

2}, Pavel V Dorovatovskii⁴, Anna V Vologzhanina¹, Ulyana S Tsareva¹, Igor E Golub^{1

2}, Ekaterina S Gulyaeva¹, Elena S Shubina¹, Georgiy B Shul'pin^{5

6}

Affiliations

¹ Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences , Vavilov Str., 28, 119991 Moscow, Russia.
² People's Friendship University of Russia , Miklukho-Maklay Str., 6, 117198 Moscow, Russia.
³ Pirogov Russian National Research Medical University , Ostrovitianov str., 1, 117997 Moscow, Russia.
⁴ National Research Center "Kurchatov Institute" , Akademika Kurchatova pl., 1, 123182 Moscow, Russia.
⁵ Semenov Institute of Chemical Physics, Russian Academy of Sciences , ulitsa Kosygina, dom 4, Moscow 119991, Russia.
⁶ Plekhanov Russian University of Economics , Stremyannyi pereulok, dom 36, Moscow 117997, Russia.

PMID: 28318235
DOI: 10.1021/acs.inorgchem.7b00061

Abstract

Three types of unusual cagelike copper(II) methylsilsesquioxanes, namely, nona- [(MeSiO_1.5)₁₈(CuO)₉] 1, hexa- [(MeSiO_1.5)₁₀(HO_0.5)₂(CuO)₆(C₁₂H₈N₂)₂(MeSiO_1.5)₁₀(HO_0.5)_1.33(CH₃COO_0.5)_0.67(CuO)₆(C₁₂H₈N₂)₂] 2, [(MeSiO_1.5)₁₀(CuO)₆(MeO_0.5)₂(C₁₀H₈N₂)₂] 3, and trinuclear [(MeSiO_1.5)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.