Bilyachenko Alexey N, Dronova Marina S, Yalymov Alexey I, Lamaty Frédéric, Bantreil Xavier, Martinez Jean, Bizet Christelle, Shul'pina Lidia S, Korlyukov Alexander A, Arkhipov Dmitry E, Levitsky Mikhail M, Shubina Elena S, Kirillov Alexander M, Shul'pin Georgiy B
Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov str., 28, Moscow 119991 (Russia).
Institut des Biomolécules Max Mousseron (IBMM), UMR 5247 CNRS-Université Montpellier-ENSCM, Bâtiment Chimie (17), Faculté des Sciences Place, Eugène Bataillon 34095 Montpellier cedex 5 (France).
Chemistry. 2015 Jun 8;21(24):8758-70. doi: 10.1002/chem.201500791. Epub 2015 May 7.
The transmetalation of bimetallic copper-sodium silsesquioxane cages, namely, [(PhSiO1.5 )10 (CuO)2 (NaO0.5 )2 ] ("Cooling Tower"; 1), [(PhSiO1.5 )12 (CuO)4 (NaO0.5 )4 ] ("Globule"; 2), and [(PhSiO1.5 )6 (CuO)4 (NaO0.5 )4 (PhSiO1.5 )6 ] ("Sandwich"; 3), resulted in the generation of three types of hexanuclear cylinder-like copper silsesqui- oxanes, [(PhSiO1.5 )12 (CuO)6 (C4 H9 OH)2 (C2 H5 OH)6 ] (4), [(PhSiO1.5 )12 (CuO)6 (C4 H8 O2 )4 (PhCN)2 (MeOH)4 ] (5), and [(PhSiO1.5 )12 (CuO)6 (NaCl)(C4 H8 O2 )12 (H2 O)2 ] (6). The products show a prominent "solvating system-structure" dependency, as determined by X-ray diffraction. Topological analysis of cages 1-6 was also performed. In addition, DFT theory was used to examine the structures of the Cooling Tower and Cylinder compounds, as well as the spin density distributions. Compounds 1, 2, and 5 were applied as catalysts for the direct oxidation of alcohols and amines into the corresponding amides. Compound 6 is an excellent catalyst in the oxidation reactions of benzene and alcohols.
双金属铜 - 钠倍半硅氧烷笼，即[(PhSiO1.5 )10 (CuO)2 (NaO0.5 )2 ]（“冷却塔”；1）、[(PhSiO1.5 )12 (CuO)4 (NaO0.5 )4 ]（“小球”；2）和[(PhSiO1.5 )6 (CuO)4 (NaO0.5 )4 (PhSiO1.5 )6 ]（“三明治”；3）的金属转移反应，生成了三种类型的六核圆柱状铜倍半硅氧烷，[(PhSiO1.5 )12 (CuO)6 (C4 H9 OH)2 (C2 H5 OH)6 ]（4）、[(PhSiO1.5 )12 (CuO)6 (C4 H8 O2 )4 (PhCN)2 (MeOH)4 ]（5）和[(PhSiO1.5 )12 (CuO)6 (NaCl)(C4 H8 O2 )12 (H2 O)2 ]（6）。通过X射线衍射确定，这些产物表现出显著的“溶剂化体系 - 结构”依赖性。还对笼1 - 6进行了拓扑分析。此外，使用密度泛函理论（DFT）研究了冷却塔和圆柱状化合物的结构以及自旋密度分布。化合物1、2和5被用作将醇和胺直接氧化为相应酰胺的催化剂。化合物6是苯和醇氧化反应中的优良催化剂。
