Nesmeyanov Institute of Organoelement Compounds , Russian Academy of Sciences , Vavilov Strasse 28 , Moscow , Russia.
Peoples' Friendship University of Russia (RUDN University) , Miklukho-Maklay Strasse 6 , Moscow , Russia.
Inorg Chem. 2018 Sep 17;57(18):11524-11529. doi: 10.1021/acs.inorgchem.8b01496. Epub 2018 Aug 30.
Unusual high-cluster (Cu) cage phenylsilsesquioxanes were obtained via complexation of in situ Cu,Na-silsesquioxane species formed with phenanthroline and neocuproine. In the first case, phenanthroline, acting as "a silent ligand" (not participating in the composition of the final product), favors the formation of an unprecedented cagelike phenylsilsesquioxane of CuNa nuclearity, 1. In the second case, neocuproine ligands withdraws two Cu ions from the metallasilsesquioxane matrix, producing two cationic fragments Cu(neocuproine). The remaining metallasilsesquioxane is rearranged into an anionic cage of CuNa nuclearity, finalizing the formation of a specific ionic complex, 2. The impressive molecular architecture of both types of complexes, e.g., the presence of different (cyclic/acyclic) types of silsesquioxane ligands, was established by single-crystal X-ray diffraction studies. Compound 1 was revealed to be highly active in the oxidative amidation of benzylic alcohol and the catalyst loading could be reduced down to 100 ppm of Cu. Catalytic studies of compound 1 demonstrated its high activity in hydroperoxidation of alkanes with HO and oxidation of alcohols to ketones with tert-BuOOH.
通过与菲啰啉和新铜试剂形成的原位 Cu，Na-硅倍半氧烷配合物，得到了不寻常的高笼（Cu）笼苯硅倍半氧烷。在第一种情况下，菲啰啉作为“沉默配体”（不参与最终产物的组成），有利于形成前所未有的 CuNa 核笼状苯硅倍半氧烷 1。在第二种情况下，新铜试剂从金属硅倍半氧烷基质中提取出两个 Cu 离子，生成两个阳离子片段 Cu(新铜试剂)。剩余的金属硅倍半氧烷重新排列成具有 CuNa 核的阴离子笼，最终形成特定的离子配合物 2。通过单晶 X 射线衍射研究确定了这两种类型的配合物的令人印象深刻的分子结构，例如存在不同（环状/非环状）类型的硅倍半氧烷配体。发现化合物 1 在苄醇的氧化氨化中具有很高的活性，催化剂负载量可降低至 100ppm 的 Cu。化合物 1 的催化研究表明其在烷烃的过氧化物氧化中具有很高的活性，以及在叔丁基过氧化物氧化醇生成酮。
