The pnictogen bond: a quantitative molecular orbital picture

• Autor(a) principal: Santos, Lucas de Azevedo
• Data de Publicação: 2021
• Outros Autores: Hamlin, Trevor A., Ramalho, Teodorico C., Bickelhaupt, F. Matthias
• Tipo de documento: Artigo
• Idioma: eng
• Título da fonte: Repositório Institucional da UFLA
• Texto Completo: http://repositorio.ufla.br/jspui/handle/1/48861
• topic: Pnictogen bonds; KS-MO; Kohn-Sham molecular orbital theory; Energy decomposition analysis (EDA); Voronoi deformation density (VDD)

We have analyzed the structure and stability of archetypal pnictogen-bonded model complexes D3Pn⋯A− (Pn = N, P, As, Sb; D, A = F, Cl, Br) using state-of-the-art relativistic density functional calculations at the ZORA-M06/QZ4P level. We have accomplished two tasks: (i) to compute accurate trends in pnictogen-bond strength based on a set of consistent data; and (ii) to rationalize these trends in terms of detailed analyses of the bonding mechanism based on quantitative Kohn–Sham molecular orbital (KS-MO) theory in combination with a canonical energy decomposition analysis (EDA) and Voronoi deformation density (VDD) analyses of the charge distribution. We have found that pnictogen bonds have a significant covalent character stemming from strong HOMO–LUMO interactions between the lone pair of A− and σ* of D3Pn. As such, the underlying mechanism of the pnictogen bond is similar to that of hydrogen, halogen, and chalcogen bonds.