Details

Autor(en) / Beteiligte

• Cao, Chun‐Shuai
• Xia, Shu‐Mei
• Song, Zhen‐Jun
• Xu, Hang
• Shi, Ying
• He, Liang‐Nian
• Cheng, Peng
• Zhao, Bin

Titel

Highly Efficient Conversion of Propargylic Amines and CO2 Catalyzed by Noble‐Metal‐Free [Zn116] Nanocages

Ist Teil von

• Angewandte Chemie International Edition, 2020-05, Vol.59 (22), p.8586-8593

Auflage

International ed. in English

Ort / Verlag

Weinheim: Wiley Subscription Services, Inc

Erscheinungsjahr

2020

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• The reaction of propargylic amines and CO2 can provide high‐value‐added chemical products. However, most of catalysts in such reactions employ noble metals to obtain high yield, and it is important to seek eco‐friendly noble‐metal‐free MOFs catalysts. Here, a giant and lantern‐like [Zn116] nanocage in zinc‐tetrazole 3D framework [Zn22(Trz)8(OH)12(H2O)9⋅8 H2O]n Trz=(C4N12O)4− (1) was obtained and structurally characterized. It consists of six [Zn14O21] clusters and eight [Zn4O4] clusters. To our knowledge, this is the highest‐nuclearity nanocages constructed by Zn‐clusters as building blocks to date. Importantly, catalytic investigations reveal that 1 can efficiently catalyze the cycloaddition of propargylic amines with CO2, exclusively affording various 2‐oxazolidinones under mild conditions. It is the first eco‐friendly noble‐metal‐free MOFs catalyst for the cyclization of propargylic amines with CO2. DFT calculations uncover that ZnII ions can efficiently activate both C≡C bonds of propargylic amines and CO2 by coordination interaction. NMR and FTIR spectroscopy further prove that Zn‐clusters play an important role in activating C≡C bonds of propargylic amines. Furthermore, the electronic properties of related reactants, intermediates and products can help to understand the basic reaction mechanism and crucial role of catalyst 1. A lantern‐like [Zn116] cage consisting of six [Zn14O21] and eight [Zn4O4] clusters represents the highest‐nuclearity nanocage assembled by Zn‐clusters to date. It is the first eco‐friendly noble‐metal‐free metal–organic framework (MOF) catalyst for the cyclization of propargylic amines with CO2.