Computational investigations of NHC-backbone configurations for applications in organocatalytic umpolung reactions

Density functional theory (DFT) and multiconfigurational self-consistent field theory (MCSCF) methods are employed to investigate variation of the electronic properties of various N-heterocyclic carbenes. Alterations to the backbone by increased or decreased conjugation, heteroatom substitution in the NHC ring, and electron-donating or -withdrawing backbone substituents are modeled. The MCSCF calculations show extensive delocalization of both the highest occupied and lowest unoccupied molecular orbitals for NHCs with polymerizable backbone substituents. The free energies of the intermediates and transition structures for benzoin condensation are also shown to be sensitive to substitution of the NHC backbone. Taken together, these results imply great sensitivity of the reactivity of poly(NHC) catalysts to backbone modification at this moiety. Implications with respect to enhancement of poly(NHC)s employed in umpolung catalysis are discussed. Computational modeling and orbital analyses reveal enhanced catalytic properties based on N-heterocyclic carbene backbone modifications.