Assessment of stereoelectronic factors that influence the CO 2 fixation ability of N-heterocyclic carbenes: A DFT study

Manjaly J. Ajitha, Cherumuttathu H. Suresh*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

67 Scopus citations


The CO 2 fixation ability of N-heterocyclic carbenes (NHC) has been assessed on the basis of electronic and steric properties of the N- and C-substituents, measured in terms of molecular electrostatic potential minimum, observed at the carbene lone pair region of NHC (V min1) as well as at the carboxylate region of the NHC-CO 2 adduct (V min2). Both V min1 and V min2 are found to be simple and efficient descriptors of the stereoelectronic effect of NHCs. The V min-based analysis also proved that the stereoelectronic effect of N- and C-substituents is additive. When only C-substituents are present in NHC, its CO 2 affinity solely depends on the electronic effect, whereas if the N-center bears the substituents, the steric factor plays a major role in the carboxylation/decarboxylation process. For standard substituents, maximum CO 2 binding energy of 18.0 kcal/mol is observed for the most electron-donating combination of NMe 2 as the C-substituent and Me as the N-substituent. Introduction of ring strain through five-membered ring fusion at the NC bond slightly increased the electron-rich character of the carbene lone pair and also enhanced the CO 2 binding energy to 20.9 kcal/mol. To further improve the CO 2 fixing ability of NHCs, we have proposed the use of CH 2OH, CH 2NHCOMe, and CH 2NHPh as N-substituents, as they participate in intramolecular hydrogen bond interaction with the carboxylate. With the new strategy, considerable improvement in the CO 2 binding energy (26.5 to 33.0 kcal/mol) is observed.

Original languageEnglish (US)
Pages (from-to)1087-1094
Number of pages8
JournalJournal of Organic Chemistry
Issue number2
StatePublished - Jan 20 2012

ASJC Scopus subject areas

  • Organic Chemistry


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