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Design, Synthesis, and Photochemical Properties of Clickable Caged Compounds
Published on: October 15, 2019
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Cu6- and Cu8-Based Acetylacetonate/Phenylsilsesquioxane Cages: Synthesis, Structure, and Activity in Oxidative
Grigorii S Astakhov1, Zhibin Huang2, Victor N Khrustalev2,3
1School of Chemistry and Chemical Engineering, State Key Laboratory of Crystal Materials, Shandong University, Ji'nan 250100, People's Republic of China.
Inorganic Chemistry
|April 15, 2026
Summary
New copper cage complexes, synthesized via self-assembly, show high efficiency as precatalysts in oxidative amidation and aniline oxidation reactions, utilizing low copper loadings.
Area of Science:
- Coordination Chemistry
- Supramolecular Chemistry
- Catalysis
Background:
- Copper complexes are versatile catalysts in organic synthesis.
- Self-assembly offers a route to intricate molecular architectures.
- Solvent effects play a crucial role in dictating the outcome of self-assembly processes.
Purpose of the Study:
- To synthesize novel copper cage complexes through solvent-controlled self-assembly.
- To investigate the structural diversity of these complexes based on nuclearity.
- To evaluate their catalytic activity in oxidative amidation and aniline oxidation.
Main Methods:
- Solvent-controlled self-assembly of phenylsiloxanolate/acetylacetonate copper precursors.
- Characterization of isolated Cu6 and Cu8 cage complexes.
- Testing precatalyst activity in oxidative amidation and aniline oxidation reactions.
Main Results:
- Two types of sandwich-type cage complexes with varying acetylacetonate ligands (two or four) were isolated based on solvent choice.
- The Cu6 and Cu8 complexes demonstrated high efficacy as precatalysts.
- The oxidative amidation reaction proceeded in good to excellent yields with 100 ppm copper loading.
- Successful oxidation of aniline to nitrobenzene using tert-butyl hydroperoxide was achieved.
Conclusions:
- Solvent-controlled self-assembly provides access to distinct copper cage architectures.
- These copper cage complexes are highly active and efficient precatalysts for key organic transformations.
- The developed catalytic systems offer a sustainable approach with low metal loading.
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