Annulated boron substituted N-heterocyclic carbenes: theoretical prediction of highly electrophilic carbenes

Abstract

Theoretical calculations were carried out to understand the effect of annulation on the electronic and ligand properties of boron substituted N-heterocyclic carbenes (B-NHCs). Annulation results in a decrease in stability as indicated by the calculated values of singlet–triplet separations and stabilization energies as well as HOMO–LUMO gaps. Annulated B-NHCs are found to be weaker σ-donors but better π-acceptors than the parent ones. The decrease in σ-donation ability and the increase in π-accepting ability are further supported by the calculated values of proton affinities, nucleophilicity and electrophilicity indices as well as ³¹P NMR chemical shifts of the corresponding NHC–PPh adducts. Most of the annulated B-NHCs are found to have significantly enhanced electrophilicity than the other known carbenes.