We found a match
Your institution may have access to this item. Find your institution then sign in to continue.
- Title
A Family of Hexacopper Phenylsilsesquioxane/Acetate Complexes: Synthesis, Solvent‐Controlled Cage Structures, and Catalytic Activity.
- Authors
Zueva, Anna Y.; Bilyachenko, Alexey N.; Arteev, Ivan S.; Khrustalev, Victor N.; Dorovatovskii, Pavel V.; Shul'pina, Lidia S.; Ikonnikov, Nikolay S.; Gutsul, Evgenii I.; Rahimov, Karim G.; Shubina, Elena S.; Reis Conceição, Nuno; Mahmudov, Kamran T.; Guedes da Silva, M. Fátima C.; Pombeiro, Armando J. L.
- Abstract
Convenient self‐assembly synthesis of copper(II) complexes via double (phenylsilsesquioxane and acetate) ligation allows to isolate a family of impressive sandwich‐like cage compounds. An intriguing feature of these complexes is the difference in the structure of a pair of silsesquioxane ligands despite identical (Cu6) nuclearity and number (four) of acetate fragments. Formation of particular combination of silsesquioxane ligands (cyclic/cyclic vs condensed/condensed vs cyclic/condensed) was found to be dependent on the synthesis/crystallization media. A combination of Si4‐cyclic and Si6‐condensed silsesquioxane ligands is a brand new feature of cage metallasilsesquioxanes. A representative Cu6‐complex (4) (with cyclic silsesquioxanes) exhibited high catalytic activity in the oxidation of alkanes and alcohols with peroxides. Maximum yield of the products of cyclohexane oxidation attained 30 %. The compound 4 was also tested as catalyst in the Baeyer‐Villiger oxidation of cyclohexanone by m‐chloroperoxybenzoic acid: maximum yields of 88 % and 100 % of ϵ‐caprolactone were achieved upon conventional heating at 50 °C for 4 h and MW irradiation at 70 or 80 °C during 30 min, respectively. It was also possible to obtain the lactone (up to 16 % yield) directly from the cyclohexane via a tandem oxidation/Baeyer‐Villiger oxidation reaction using the same oxidant.
- Subjects
CATALYTIC activity; BAEYER-Villiger rearrangement; CATALYTIC oxidation; ACETATES; CATALYST testing; CYCLOHEXANONES; ALCOHOL oxidation; CLATHRATE compounds; COPPER compounds
- Publication
Chemistry - A European Journal, 2024, Vol 30, Issue 31, p1
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.202401164