Theoretical study of the bonding between aminocarbene and main group elements

Abstract

B3LYP/6-31G* calculations were carried out on adducts formed by the interaction of a cyclic unsaturated aminocarbene with carbenoid moieties CH₂, SiH₂, NH, PH, O or S. The bonding mode has been described using the Natural Bond Orbital (NBO) partitioning schemes, the Charge-Decomposition Analysis (CDA) and the topological analysis of the Electron Localization Function (ELF). A donor–acceptor interaction with a substantial π back-bonding of the carbenoid moiety is observed in the case of CH₂, SiH₂, PH and S. The bond-description has been correlated with the bond length, the bond dissociation energy and the aromaticity of the carbene ring obtained by Nucleus-Independent Chemical Shift (NICS) calculation.