title: Structure and bonding of novel acyclic bisaminoarsenium cations.
abstract: The synthesis and characterization of a salt bearing a labile bisaminoarsenium cation of the type {[(Me3Si)2N]2As}(+) (9a) are described, which was obtained in the reaction of the chloroarsane [(Me3Si)2N]2AsCl (8) with GaCl3. Reacting 8 with AgOTf did not yield an arsenium salt, but the cyclo-diarsadiazane [(Me3Si)2NAs-μ-NSiMe3]2 (11) was obtained in excellent yields. Moreover, the reactivity of the analogous antimony species [(Me3Si)2N]2SbCl (12) was studied. In the reaction with GaCl3, the aminochlorostibenium salt [(Me3Si)2NSbCl](+)[(Me3Si)2N(GaCl3)2](-) (5) was isolated. In the reaction with AgOTf, substitution of the chlorine in 12 resulted in the formation of [(Me3Si)2N]2SbOTf (13), a compound with significant stibenium character. All new compounds have been fully characterized by means of X-ray, vibrational spectroscopy, CHN analysis, and NMR experiments. All compounds were further investigated by means of density functional theory and the bonding situation was accessed by natural bond orbital (NBO) analysis.
authors.affiliation: Abteilung Anorganische Chemie, Institut für Chemie, Universität Rostock, Albert-Einstein-Strasse 3a, 18059 Rostock, Germany.
authors.forename: Christian
authors.initials: C
authors.lastname: Hering
authors.forename: Julia
authors.initials: J
authors.lastname: Rothe
authors.forename: Axel
authors.initials: A
authors.lastname: Schulz
authors.forename: Alexander
authors.initials: A
authors.lastname: Villinger