A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Str. 28, 119991 Moscow, Russia.
Higher Chemical College, Mendeleev University of Chemical Technology of Russia, Miusskaya Sq. 9, 125047 Moscow, Russia.
Molecules. 2023 Jan 26;28(3):1211. doi: 10.3390/molecules28031211.
A family of unusual octacopper cage methylsilsesquioxanes - were prepared and characterized. Features of their cagelike (prismatic) structure were established using X-ray diffraction studies. Effects of distortion of prismatic cages - due to variation of (i) additional alkaline metal ions (K, Rb, or Cs), (ii) combination of solvating ligands, and (iii) nature of encapsulating species were found. Opportunities for the design of supramolecular 1D extended structures were found. These opportunities are based on (i) formate linkers between copper centers (in the case of CuK-based compound ) or (ii) crown ether-like contacts between cesium ions and siloxane cycles (in the case of CuCs-based compound ). CuCs-complex was evaluated in the catalysis of alkanes and alcohols. Complex exhibits high catalytic activity. The yield of cyclohexane oxidation products is 35%. The presence of nitric acid is necessary as a co-catalyst. The oxidation of alcohols with the participation of complex as a catalyst and tert-butyl hydroperoxide as an oxidizer also proceeds in high yields of up to 98%.
一种新型的十八铜笼甲基倍半硅氧烷被制备并进行了结构表征。通过 X 射线衍射研究确定了笼状（棱柱形）结构的特征。研究了由于（i）额外的碱金属离子（K、Rb 或 Cs）、（ii）溶剂化配体的组合以及（iii）包封物种的性质的变化导致棱柱形笼的变形。发现了设计超分子 1D 延伸结构的机会。这些机会基于（i）铜中心之间的甲酸盐连接体（在基于 CuK 的化合物的情况下）或（ii）铯离子和硅氧烷环之间的冠醚样接触（在基于 CuCs 的化合物的情况下）。对 CuCs 配合物在烷烃和醇的催化作用进行了评价。该配合物表现出很高的催化活性。环己烷氧化产物的收率为 35%。需要硝酸作为助催化剂。在催化剂为复合 物和叔丁基过氧化氢作为氧化剂的情况下，醇的氧化也以高达 98%的收率进行。
