Cage-like manganesesilsesquioxanes: features of their synthesis, unique structure, and catalytic activity in oxidative amidations

Grigorii S. Astakhov, Victor N. Khrustalev, Marina S. Dronova, Evgenii I. Gutsul, Alexander A. Korlyukov, Dmitri Gelman*, Yan V. Zubavichus, Daniil A. Novichkov, Alexander L. Trigub, Elena S. Shubina, Alexey N. Bilyachenko*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

10 Scopus citations

Abstract

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).

Original languageAmerican English
Pages (from-to)4525-4537
Number of pages13
JournalInorganic Chemistry Frontiers
Volume9
Issue number17
DOIs
StatePublished - 14 Jul 2022

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© 2022 The Royal Society of Chemistry.

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