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).