Comprehensive Basicity Scales for N‐Heterocyclic Carbenes in DMSO: Implications on the Stabilities of N‐Heterocyclic Carbene and CO₂ Adducts

Abstract

A very broad acidity scale (≈40 pK units) for about 400 N-heterocyclic carbene precursors (NHCPs) with various backbones and electronic features, including imidazolylidenes, 1,2,4-triazolylidenes, cyclic diaminocarbenes (CDACs), diamidocarbenes (DACs), thiazolylidenes, cyclic (alkyl)(amino)carbenes (CAACs) and mesoionic carbenes (MICs), was established in DMSO by a well examined computational method. Varying the backbone structure or flanking N-substituents can have different extent of acidifying effects, depending on both the nature and number of substituent(s). The Gibbs energies (ΔG_r s) for the reactions between the corresponding NHCs and CO₂ were also calculated. There is a good linear correlation between the pK_a s of most NHCPs and ΔG_r s, suggesting that a greater basicity of NHC leads to a more stable NHC-CO₂ adduct. Interestingly, the nearby asymmetric environment has virtually no differential effect on the acidities of the chiral NHCP enantiomers, but has a pronounced effect on the ΔG_r values.