Bilyachenko Alexey N, Arteev Ivan S, Khrustalev Victor N, Shul'pina Lidia S, Korlyukov Alexander A, Ikonnikov Nikolay S, Shubina Elena S, Kozlov Yuriy N, Reis Conceição Nuno, Guedes da Silva M Fátima C, Mahmudov Kamran T, Pombeiro Armando J L
A.N.Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Street, 28, Moscow 119991, Russia.
Peoples' Friendship University of Russia, Miklukho-Maklay St., 6, Moscow 117198, Russia.
Inorg Chem. 2023 Aug 21;62(33):13573-13586. doi: 10.1021/acs.inorgchem.3c01989. Epub 2023 Aug 10.
A small family of nonanuclear CuCs-based phenylsilsesquioxanes - were prepared by a convenient self-assembly approach and characterized by X-ray diffraction studies. The compounds and show some unprecedented structural features such as the presence of a [PhSiO] silsesquioxane ligand and a CuCs nuclearity in which the metal cations occupy unusual positions within the cluster. Copper ions are "wrapped" into a silsesquioxane matrix, while cesium ions are located in external positions. This resulted in cesium-involved aggregation of coordination polymer structures. Both compounds and realize specific metallocene (cesium-phenyl) linkage between neighboring cages. Compound is evaluated as a catalyst in the Baeyer-Villiger (B-V) oxidation of cyclohexanone and tandem cyclohexane oxidation/B-V oxidation of cyclohexanone with -chloroperoxybenzoic acid (mCPBA) as an oxidant, in an aqueous acetonitrile medium, and HNO as the promoter. A quantitative yield of ε-caprolactone was achieved under conventional heating at 50 °C for 4 h or MW irradiation for 30 min (for cyclohexanone as substrate); 17 and 19% yields of lactone upon MW irradiation at 80 °C for 30 min and heating at 50 °C for 4 h, respectively (for cyclohexane as a substrate), were achieved. Complex was evaluated as a catalyst for the oxidation of alkanes to alkyl hydroperoxides and alcohols to ketones with peroxides at 60 °C in acetonitrile. The maximum yield of cyclohexane oxidation products was 30%. Complex exhibits high activity in the oxidation of alcohols.
通过一种简便的自组装方法制备了一小族基于九核铜铯的苯基倍半硅氧烷，并通过X射线衍射研究对其进行了表征。化合物 和 展现出一些前所未有的结构特征，例如存在[PhSiO]倍半硅氧烷配体以及铜铯核数，其中金属阳离子在簇内占据不寻常的位置。铜离子被“包裹”在倍半硅氧烷基质中，而铯离子位于外部位置。这导致了涉及铯的配位聚合物结构的聚集。化合物 和 均实现了相邻笼之间特定的金属茂（铯 - 苯基）连接。化合物 在水乙腈介质中，以 - 氯过氧苯甲酸（mCPBA）为氧化剂、HNO为促进剂的情况下，被评估为环己酮的拜耳 - 维利格（B - V）氧化以及环己酮的串联环己烷氧化/B - V氧化反应的催化剂。在50℃常规加热4小时或微波辐射30分钟（以环己酮为底物）的条件下，实现了ε - 己内酯的定量产率；在80℃微波辐射30分钟和50℃加热4小时（以环己烷为底物）的条件下，内酯产率分别为17%和19%。配合物 被评估为在乙腈中60℃下用过氧化物将烷烃氧化为烷基氢过氧化物以及将醇氧化为酮的催化剂。环己烷氧化产物的最大产率为30%。配合物 在醇的氧化反应中表现出高活性。
