Combination of Phenylsilsesquioxane and Acetate Ligands as an Approach to a Record High Nuclear Cu<sub>13</sub>Na<sub>2</sub>‐Cage. Synthesis, Unique Structure, and Catalytic Activity
Self-assembly synthesis of mixed-ligand (silsesquioxane/acetate) complex allows to isolate record high nuclear copper(II) Cu<sub>13</sub>-cage (1). In the presence of two additional sodium ions, a unique molecular architecture, with triple combination of ligands (cyclic and acyclic silsesquioxanes as well as acetates), has been formed. The structure was established by single-crystal X-ray diffraction based on the use of synchrotron radiation. Complex 1 was evaluated as precatalyst in the Baeyer-Villiger oxidation of cyclohexanone towards ϵ-caprolactone, employing hydrogen peroxide, tert-butyl hydroperoxide (TBHP) or m-chloroperoxybenzoic acid (mCPBA) as oxidants, in an aqueous acidic acetonitrile medium. The direct formation of the lactone from cyclohexane via a tandem peroxidative oxidation/Baeyer-Villiger oxidation was also studied. For both substrates, the best results (ϵ-caprolactone yields up to 100 % or 26 %, from cyclohexanone or cyclohexane, respectively) were achieved with mCPBA under considerably mild conditions, i. e., conventional heating at 50 °C for 4 h or microwave (MW) irradiation at 80 °C for only 30 minutes.
Authors
- Victor N. Khrustalev (ORCID: https://orcid.org/0000-0001-8806-2975)
- Nuno Reis Conceição (ORCID: https://orcid.org/0000-0001-5102-8482)
- Н. Н. Лобанов (ORCID: https://orcid.org/0000-0002-1954-2809)
- Karim Ragimov (ORCID: https://orcid.org/0000-0002-9658-4105)
- Павел В. Дороватовский (ORCID: https://orcid.org/0000-0002-2978-3614)
- Elena S. Shubina (ORCID: https://orcid.org/0000-0001-8057-3703)
- Armando J. L. Pombeiro (ORCID: https://orcid.org/0000-0001-8323-888X)
- Аlexey N. Bilyachenko (ORCID: https://orcid.org/0000-0003-3136-3675)
- Zhi Wang (ORCID: https://orcid.org/0000-0001-8315-3501)
- Abdallah G. Mahmoud (ORCID: https://orcid.org/0000-0002-8212-2102)
- Zhibin Huang
Institutions
- Peoples' Friendship University of Russia (RU)
- University of Lisbon (PT)
- Shandong University (CN)
- Baku State University (AZ)
- Kurchatov Institute (RU)
- A. N. Nesmeyanov Institute of Organoelement Compounds (RU)
- Institut des Sciences Moléculaires (FR)
- N.D. Zelinsky Institute of Organic Chemistry (RU)
- Experimental Station (US)
- Rede de Química e Tecnologia (PT)
- Universidade Nova de Lisboa (PT)
- Helwan University (EG)
Publication Details
- Journal
- Chemistry - A European Journal
- Published
- 2024-12-10
- DOI
- https://doi.org/10.1002/chem.202403604
- Citations
- 3
- Primary Topic
- Magnetism in coordination complexes
- Type
- article
- Field-Weighted Citation Impact
- 0.35
Funders
- Russian Science Foundation
- Ministry of Science and Higher Education of the Russian Federation
- Centro de Química Estrutural
- Fundação para a Ciência e a Tecnologia