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Theoretical Studies on Muti‐Hydroxyimides as Highly Efficient Catalysts for Aerobic Oxidation
Author(s) -
Chen Kexian,
Jia Lu,
Dao Rina,
Yao Jia,
Wang Congmin,
Chen Zhirong,
Li Haoran
Publication year - 2013
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201200865
Subject(s) - radical , catalysis , chemistry , rational design , photochemistry , solvent , combinatorial chemistry , organic chemistry , nanotechnology , materials science
N , N ‐dihydroxypyromellitimide (NDHPI) and N , N ′, N ′′ ‐ trihydroxyisocyanuric acid (THICA) have been recently demonstrated to act as better carbon‐radical‐producing catalysts than the popular N ‐hydroxyphthalimide (NHPI). To gain a mature understanding of these particular catalysts, herein their geometrical, electronic, and thermochemical properties, as well as their catalytic activities, have been systemically investigated by a theoretical analysis. It appears that THICA, unlike NDHPI and NHPI, is unsuitable for solvent‐free catalysis or catalysis in aprotic solvents due to its favorable coexistent planar conformer. Besides, the more remarkable catalytic efficiencies of NDHPI and THICA compared to NHPI can be ascribed to the lower barriers and the endothermicity in the H‐abstraction processes by their radicals, especially by their multi‐radicals which show stronger electron‐withdrawing effects. Furthermore, the generation of THICA radicals would be much feasible at high temperature without co‐catalysts. This study provides a new perspective towards the rational design of reactive hydroxyimide organocatalysts for industrial applications.