Carbon dioxide forms covalent complexes with N-heterocyclic carbenes. These complexes are of interest in catalysis as well as for their potential use in various carbon capture and storage strategies. A previous report showed that the stability of one such complex, N,N-dimethylimidazolium 2-carboxylate, was remarkably sensitive to solvent polarity. Polar environments lead to a kinetically stronger, shorter, and more polar bond between the carbene and CO2. The current study shows that this solvent effect is general across a wide range of NHC complexes with CO2. Computational modeling at the DFT level shows that the lability of these bonds can be controlled by steric pressure due to substituents on the heteroatoms flanking the carbene center, as well as inductive electronic effects from substituents on the C4 and C5 positions. Moreover, a strong correlation between the gas-phase NHC-CO2 bond distance and the Gibbs free energy barrier for decarboxylation is demonstrated.