Polyazide Chemistry Preparation and Characterization of As(N3)5, Sb(N3)5 and P(C6H5)4Sb(N3)6

摘要

The binary arsenic- and antimony azide species AS(N3)3, As(N3)4+, As(N3)4-, As(N3)6-, Sb(N3)3, Sb(N3)4+, Sb(N3)4- and Sb(N3)6- have previously been reported, and the crystal structures of As(N3)3, Sb(N3)3 and As(N3)6- were determined. In addition, the Lewis based stabilized species M(N3)5-LB (M=As,Sb; LB=pyridine, quinoline NH3, N2H4, NH2CN) were published. However, previous attempts to obtain the neat pentaazides of arsenic and antimony were not successful. Even at low temperatures, attempted syntheses resulted in explosions that were described as 'so intense that only pulverized glass remained.' Furthermore, As(N3)5 was predicted to be a 'highly unstable compound,' based on its analogy to AsCl5. In this paper, we wish to communicate the synthesis and characterization of neat As(N3)5 and Sb(N3)5, and their conversion to the As(N3)6 and Sb(N3)6 anions, respectively. We also report the crystal structure of P(C6H5)4Sb(N3)6.