Computational and experimental investigations of CO₂and N₂O fixation by sterically demanding N-heterocyclic carbenes (NHC) and NHC/borane FLP systems

Abstract

The sterically demanding NHCs 1,3-di-tert-butylimidazolin-2-ylidene (1a), 1,3-di-tert-butyl-4,5-dimethylimidazolin-2-yildene (1b), and also the corresponding frustrated Lewis pair combinations 1a,b/B(C6F5)3 react readily with CO2 to form the NHC·CO2 (5a,b) and the NHC·CO2·B(C6F5)3 (9a,b) adducts, respectively. However, N2O activation and isolation of the NHC·N2O adduct (6) was only possible for NHC 1a. On heating, the NHC·N2O adduct 6 degrades to 1a, N2O, N2 and the urea derivative 7. Nevertheless, an NHC·N2O adduct of 1b was obtained with the FLP system 1b/B(C6F5)3. In contrast, for the FLP combination 1a/B(C6F5)3, N2O coordination appears to be slower than the self-deactivation. Hence, only the self-deactivation product 3 was observed under an N2O atmosphere. DFT calculations give insights into the CO2 and N2O activation process with 1a,b and 1a,b/B(C6F5)3.