1582284-05-6Relevant articles and documents
Azidophosphenium cations: Versatile reagents in inorganic synthesis
Hering, Christian,Hertrich, Maximilian,Schulz, Axel,Villinger, Alexander
, p. 3880 - 3892 (2014)
This work describes the synthesis and characterization of a series of iminophosphorane-substituted phosphenium cations of the type [R 2NPNP(Cl)2NPNR′2][GaCl4] [R = iPr; R′ = iPr (7[GaCl4]), SiMe3 (8)], which are directly derived from azidophosphenium salt [iPrNPN3][GaCl 4] (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][GaCl 4] (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 31P NMR spectroscopy. The reaction of 2SiMe3[GaCl4] with [(Me3Si)2NPCl] [GaCl4] (1SiMe3[GaCl4]) yielded an unprecedented bicyclic 1,3,2λ3,4λ5- 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[GaCl 4] (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.
