Kinetically Stabilized Diarylpnictogenium Ions

Chempluschem. 2023 Mar;88(3):e202200429. doi: 10.1002/cplu.202200429. Epub 2023 Jan 20.

Abstract

The newly prepared and fully characterized stibenium and bismuthenium ions [Rind MesE]+ (E=Sb, Bi; Rind =dispiro[fluorene-9,3'-(1',1',7',7'-tetramethyl-s-hydrindacen-4'-yl)-5',9''-fluorene) were rigorously compared to the previously communicated phosphenium and arsenium ions (E=P, As) as well as the bis(m-terphenyl) pnictogenium ions [(2,6-Mes2 C6 H3 )2 E]+ (E=Sb, Bi). It is demonstrated that the choice of the aryl substituents dramatically effects the molecular structures (e. g. the primary E-C bond lengths) and the electronic structures (e. g. the energy of the LUMOs).

Keywords: Lewis acids; carbene analogues; cations; electronic structure; pnictogens.