Cagelike Manganesesilsesquioxanes. Features of Synthesis, Unique Structure, and Catalytic Activity in Oxidative Amidations

Авторы: Astakhov Grigorii, Khrustalev Victor N., Dronova Marina, Gutsul Evgenii I., Korlyukov Alexander, Gelman Dmitri, Zubavichus Yan V., Novichkov Daniil, Trigub Alexander, Shubina Elena, Bilyachenko Alexey
Журнал: INORGANIC CHEMISTRY FRONTIERS
Том: 9
Номер: 17
Год издания: 2022
Первая страница: 4525
Последняя страница: 4537
DOI: 10.1039/d2qi01054b
Аннотация: An extended series of Mn-based cagelike phenylsilsesquioxanes 1-5 were obtained via convenient self-assembly reactions and complexations with 1,10-phenanthroline. Structural features of these cage complexes such as ((i) various nuclearities and types of silsesquioxane ligands, (ii) encapsulations of hydroxide and chloride species, (iii) spontaneous oxidations of MnII to MnIII) are established by single-crystal X-ray diffraction, including the use of synchrotron radiation. One of the synthesized compounds represents a unique feature among metallacomplexes – the presence of three metal ions with different oxidation states (NaI, MnII, MnIII). Furthermore, the first-ever evaluation of Mn-silsesquioxanes as precatalysts in oxidative amidation (OA) reactions allowed to develop a very effective protocol of OA of alcohols and aldehydes with low loading of Mn (5 mol % and 2.5 mol %, respectively).
Добавил в систему: Шубина Елена Соломоновна

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