Theoretical characterization of molecular complexes formed between triplet vinyl nitrene and lewis acids

Abstract

In the current work, the complexes formed between triplet vinyl nitrene (3CH2CHN) and some Lewis acids YA (LiH, LiF, BeH2, BeF2, BH3, BF3, ClH, ClF, HCl, HF) have been investigated through calculations of the electronic structure. These calculations have been carried out in order to determine the energetic stability of the N···Y (with Y = Li, Be, B, Cl, H) interactions and also to understand their chemical nature. Quantum chemical calculations predict that the molecular complexes 3CH2CHN···Y–A are always more stable than the separated 3CH2CHN and Y–A species. The interaction energies range from −0.98 kcal mol−1 (in CH2=CHN···ClH) to −39.03 kcal mol−1 (in CH2=CHN···BH3) at the CCSD(T)/6-311++G(2d,2p) level of theory. Accordingly, some of these complexes may serve to experimentally detect and characterize the elusive triplet vinyl nitrene species. Moreover, AIM theory, in particular the L(r) = −¼∇2 ρ(r) function, reveals that the N···Y interactions established between the electron lone pair of the nitrogen atom and the charge density depletion region of the Y atom are mainly of electrostatic character.