Bilyachenko Alexey N, Kulakova Alena N, Levitsky Mikhail M, Petrov Artem A, Korlyukov Alexander A, Shul'pina Lidia S, Khrustalev Victor N, Dorovatovskii Pavel V, Vologzhanina Anna V, Tsareva Ulyana S, Golub Igor E, Gulyaeva Ekaterina S, Shubina Elena S, Shul'pin Georgiy B
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.
Inorg Chem. 2017 Apr 3;56(7):4093-4103. doi: 10.1021/acs.inorgchem.7b00061. Epub 2017 Mar 20.
Three types of unusual cagelike copper(II) methylsilsesquioxanes, namely, nona- [(MeSiO)(CuO)] 1, hexa- [(MeSiO)(HO)(CuO)(CHN)(MeSiO)(HO)(CHCOO)(CuO)(CHN)] 2, [(MeSiO)(CuO)(MeO)(CHN)] 3, and trinuclear [(MeSiO)(CuO)(CHN)] 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 HO to alkyl hydroperoxides in acetonitrile.
三种不同寻常的笼状铜（II）甲基倍半硅氧烷，即九聚体[（MeSiO）（CuO）]₁、六聚体[（MeSiO）（HO）（CuO）（CHN）（MeSiO）（HO）（CHCOO）（CuO）（CHN）]₂、[（MeSiO）（CuO）（MeO）（CHN）]₃和三核体[（MeSiO）（CuO）（CHN）]₄，其产率分别为44%、27%、20%和16%。产物的核数和结构形式由溶剂体系和配体的选择控制，特别是有助于笼状结构的组装。通过单晶X射线衍射分析确定了1-4的结构。化合物1和4是首例笼状金属倍半硅氧烷，分别含有九个和三个铜离子。产物1是首次观察到的九核金属倍半硅氧烷。基于两个稠合的五元硅氧烷环，4的独特结构代表了一种此前未知的分子几何类型。提供了产物1-4中金属簇的拓扑分析。配合物1在乙腈中能有效地催化用叔丁基过氧化氢（TBHP）将醇氧化为酮，或用HO将醇氧化为烷基氢过氧化物生成烷烃。
