title: Azidophosphenium cations: versatile reagents in inorganic synthesis.
abstract: This work describes the synthesis and characterization of a series of iminophosphorane-substituted phosphenium cations of the type [R2NPNP(Cl)2NPNR'2][GaCl4] [R = iPr; R' = iPr (7[GaCl4]), SiMe3 (8)], which are directly derived from azidophosphenium salt [iPrNPN3][GaCl4] (2iPr[GaCl4]) and the corresponding chlorophosphane R2NPCl2. The reactivity of 7[GaCl4] toward 2,3-dimethylbutadiene (dmb) and 2,2'-bipyridine (bipy) was investigated, resulting in the formation of 7-dmb[GaCl4] and 7-Cl. In addition, self-condensation of [(Me3Si)2NPN3][GaCl4] (2SiMe3[GaCl4]) was studied in detail, and [(Me3Si)2NPNP(XY)N(SiMe3)2][GaCl4] [X = Cl; Y = Cl (13), N3 (14)] were determined as products on the basis of (31)P NMR spectroscopy. The reaction of 2SiMe3[GaCl4] with [(Me3Si)2NPCl][GaCl4] (1SiMe3[GaCl4]) yielded an unprecedented bicyclic 1,3,2λ(3),4λ(5)-diazadiphosphetidine (15), which was formed via a GaCl3-assisted Me3SiCl elimination starting from 13. Furthermore, cations of the type [R2NPNPR'3][GaCl4] [R = iPr; R' = cHex (19)] were obtained by the effective combination of 2R[GaCl4] (R = iPr, SiMe3) with PR'3 (R' = Ph, cHex). Azidochlorophosphanes R2NP(N3)Cl [R = iPr, SiMe3 (20R)] are shown to be accessible when 2R[GaCl4] was combined with bipy. All new compounds were 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 analysis.
authors.affiliation: Institut für Chemie, Abteilung Anorganische Chemie, Universität Rostock , Albert-Einstein-Strasse 3a, 18059 Rostock, Germany.
authors.forename: Christian
authors.initials: C
authors.lastname: Hering
authors.forename: Maximilian
authors.initials: M
authors.lastname: Hertrich
authors.forename: Axel
authors.initials: A
authors.lastname: Schulz
authors.forename: Alexander
authors.initials: A
authors.lastname: Villinger