Theoretical Study on the Effect of Annelation and Carbonylation on the Electronic and Ligand Properties of <i>N</i>‑Heterocyclic Silylenes and Germylenes: Carbene Comparisons begin To Break Down

Abstract

Quantum chemical calculations have been carried out to investigate the effect of annelation and carbonylation on the electronic and ligand properties of <i>N</i>-heterocyclic silylenes and germylenes. The thermodynamic stability of these ligands has been found to increase with annelation, while the reverse is true for carbonylation. This is in sharp contrast to N-heterocyclic carbenes (NHCs) where annelation leads to a decrease in their thermodynamic stabilities. Compared to nonannelated derivatives, annelated and carbonylated ones are found to be weaker σ donors but better π acceptors. The effect of carbonylation is more pronounced than annelation toward increasing the π acidity of these ligands. Carbonylation at the α-position with respect to the N atom attached to the Si/Ge center has been found to be the most effective way of enhancing the π acidity of these ligands. The computed natural charges reveal that electrophilicity increases upon both annelation and carbonylation. The calculated values of ³¹P NMR chemical shifts of corresponding phosphinidene adducts of these ligands have been found to correlate well with the π acidity of these Si/Ge centers