4.5 Article

Kinetically Stabilized Diarylpnictogenium Ions

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CHEMPLUSCHEM
卷 88, 期 3, 页码 -

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WILEY-V C H VERLAG GMBH
DOI: 10.1002/cplu.202200429

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carbene analogues; cations; electronic structure; Lewis acids; pnictogens

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This article compares the newly prepared and fully characterized stibenium and bismuthenium ions with previously communicated phosphenium and arsenium ions and bis(m-terphenyl) pnictogenium ions, finding that the choice of aryl substituents significantly affects molecular and electronic structures.
The newly prepared and fully characterized stibenium and bismuthenium ions [R(ind)MesE](+) (E=Sb, Bi; R-ind=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-Mes(2)C(6)H(3))(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).

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