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Oxidation Ability of CO 2 for the Transformation of Cinnamic Aldehydes to Acids Catalyzed by N‐Heterocyclic Carbene: Combining Computational and Experimental Studies
Author(s) -
Ren Xingye,
Yuan Yanli,
Ju Yan,
Wang Hongming
Publication year - 2012
Publication title -
chemcatchem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.497
H-Index - 106
eISSN - 1867-3899
pISSN - 1867-3880
DOI - 10.1002/cctc.201200529
Subject(s) - carbene , nucleophile , chemistry , catalysis , activation energy , photochemistry , reaction mechanism , activation barrier , medicinal chemistry , computational chemistry , organic chemistry
The mechanism of the CO 2 splitting reaction with N‐heterocyclic carbene (NHC) as a catalyst and cinnamic aldehydes as the oxygen acceptor was thoroughly investigated at the B3LYP/6‐31G(d,p) level. Owing to its nucleophilicity, NHC can initiate the reaction through two distinct channels (I and II) by nucleophilic attack. The results reveal that without the assistance by H 2 O, channel II is slightly more favorable than channel I, and the reaction path II‐D is the optimum reaction path. However, the reaction is difficult to conduct at room temperature because of its high activation energy barrier. Although the results suggest that most of the high activation energy barriers involved in proton transfer decrease if the reaction is assisted by H 2 O, all highest energy barriers for all reaction channels are still above 40 kcal mol −1 . This indicates that this reaction cannot be performed at room temperature, which is also proven by experiments.