In:
Angewandte Chemie, Wiley, Vol. 134, No. 35 ( 2022-08-26)
Abstract:
In enzymes, the active site residues function differently to promote chemical reactions. Such a role‐specialized division of labor has been rarely realized by synthetic catalysts. We report herein on catalytic CO 2 reduction with Fe porphyrins decorated with two cationic N,N,N ‐trimethylbenzylamine groups in cis ‐ or trans ‐arrangement. The cis ‐isomer outperforms the trans ‐isomer and reaches a TOF max of 4.4×10 5 s −1 in acetonitrile using phenol proton source. Theoretical studies revealed that the two cationic units in the cis ‐isomer are more effective than a single cationic unit to improve the CO 2 binding, and more importantly, they function differently but cooperatively to promote the C−O bond cleavage: one interacts with the CO 2 ‐adduct, while the other one interacts with the phenol molecule through electrostatic interactions. This work therefore presents a significant example of synthetic catalysts, which boost chemical reactions using a role‐specialized strategy for substrate activation.
Type of Medium:
Online Resource
ISSN:
0044-8249
,
1521-3757
DOI:
10.1002/ange.v134.35
DOI:
10.1002/ange.202209602
Language:
English
Publisher:
Wiley
Publication Date:
2022
detail.hit.zdb_id:
505868-5
detail.hit.zdb_id:
506609-8
detail.hit.zdb_id:
514305-6
detail.hit.zdb_id:
505872-7
detail.hit.zdb_id:
1479266-7
detail.hit.zdb_id:
505867-3
detail.hit.zdb_id:
506259-7
Permalink