TY - JOUR
T1 - Cage-like manganesesilsesquioxanes
T2 - features of their synthesis, unique structure, and catalytic activity in oxidative amidations
AU - Astakhov, Grigorii S.
AU - Khrustalev, Victor N.
AU - Dronova, Marina S.
AU - Gutsul, Evgenii I.
AU - Korlyukov, Alexander A.
AU - Gelman, Dmitri
AU - Zubavichus, Yan V.
AU - Novichkov, Daniil A.
AU - Trigub, Alexander L.
AU - Shubina, Elena S.
AU - Bilyachenko, Alexey N.
N1 - Publisher Copyright:
© 2022 The Royal Society of Chemistry.
PY - 2022/7/14
Y1 - 2022/7/14
N2 - An extended series of Mn-based cage-like phenylsilsesquioxanes were obtained via convenient self-assembly reactions and complexations with 1,10-phenanthroline. The structural features of these cage complexes such as (i) various nuclearities and types of silsesquioxane ligands, (ii) encapsulations of hydroxide and chloride species, and (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, and MnIII). Furthermore, the first-ever evaluation of Mn-silsesquioxanes as precatalysts in oxidative amidation (OA) reactions allowed us to develop a very effective protocol of OA of alcohols and aldehydes with low loading of Mn (5 mol% and 2.5 mol%, respectively).
AB - An extended series of Mn-based cage-like phenylsilsesquioxanes were obtained via convenient self-assembly reactions and complexations with 1,10-phenanthroline. The structural features of these cage complexes such as (i) various nuclearities and types of silsesquioxane ligands, (ii) encapsulations of hydroxide and chloride species, and (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, and MnIII). Furthermore, the first-ever evaluation of Mn-silsesquioxanes as precatalysts in oxidative amidation (OA) reactions allowed us to develop a very effective protocol of OA of alcohols and aldehydes with low loading of Mn (5 mol% and 2.5 mol%, respectively).
UR - http://www.scopus.com/inward/record.url?scp=85134852954&partnerID=8YFLogxK
U2 - 10.1039/d2qi01054b
DO - 10.1039/d2qi01054b
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AN - SCOPUS:85134852954
SN - 2052-1545
VL - 9
SP - 4525
EP - 4537
JO - Inorganic Chemistry Frontiers
JF - Inorganic Chemistry Frontiers
IS - 17
ER -