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Highly Efficient and Selective N‐Formylation of Amines with CO 2 and H 2 Catalyzed by Porous Organometallic Polymers
Author(s) -
Shen Yajing,
Zheng Qingshu,
Chen ZheNing,
Wen Daheng,
Clark James H.,
Xu Xin,
Tu Tao
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202011260
Subject(s) - formylation , catalysis , formic acid , chemistry , iridium , polymer , group 2 organometallic chemistry , adsorption , dimethylformamide , heterogeneous catalysis , combinatorial chemistry , organic chemistry , polymer chemistry , molecule , solvent
The valorization of carbon dioxide (CO 2 ) to fine chemicals is one of the most promising approaches for CO 2 capture and utilization. Herein we demonstrated a series of porous organometallic polymers could be employed as highly efficient and recyclable catalysts for this purpose. Synergetic effects of specific surface area, iridium content, and CO 2 adsorption capability are crucial to achieve excellent selectivity and yields towards N‐formylation of diverse amines with CO 2 and H 2 under mild reaction conditions even at 20 ppm catalyst loading. Density functional theory calculations revealed not only a redox‐neutral catalytic pathway but also a new plausible mechanism with the incorporation of the key intermediate formic acid via a proton‐relay process. Remarkably, a record turnover number (TON=1.58×10 6 ) was achieved in the synthesis of N,N‐dimethylformamide (DMF), and the solid catalysts can be reused up to 12 runs, highlighting their practical potential in industry.