Theoretical study of the bonding between aminocarbene and main group elements

Gilles Frison (1) , Alain Sevin (1)

1 LCT - Laboratoire de chimie théorique

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 backbonding 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.

Mots clés: N-HETEROCYCLIC CARBENES; METAL ALKYLIDENE COMPLEXES; ELECTRON LOCALIZATION FUNCTION (ELF); CRYSTALLINE CARBENE; STABLE CARBENES; ADDUCT; AROMATICITY; PHOSPHINIDENE

Domaines: Chimie théorique et/ou physique; Chimie organique

Gilles Frison, Alain Sevin. Theoretical study of the bonding between aminocarbene and main group elements. Journal of the Chemical Society Perkin Transactions 2, 2002, pp.1692-1697. ⟨10.1039/b204688a⟩. ⟨hal-00463354⟩