Binary Polyazides of Cadmium and Mercury

Following our interest in binary element–nitrogen compounds we report here on the synthesis and comprehensive characterization (M.p., IR/Raman, elemental analysis, ¹⁴N/¹³³Cd/¹⁹⁹Hg NMR) of tri‐ and tetraazido cadmate and mercurate anions E(N₃)_(2+n)]^n? (E=Cd, Hg; n=1, 2) in a series of Ph₄P]⁺ and PNP]⁺ (PNP]⁺=bis(triphenylphosphine)iminium) salts. The azide/chloride exchange in CH₂Cl₂ as well as the formation of tetrazolate salts in CH₃CN solutions of the polyazido mercurates were investigated. Single crystal X‐ray structures of all new compounds, and for comparison Ph₄P]Cd₂(N₃)₅(H₂O)], were determined. Moreover, the synthesis of anhydrous cadmium(II) azide and its DMSO adduct is presented for the first time. For a better understanding of structure and bonding in E(N₃)₂, E(N₃)₃]^? and E(N₃)₄]^2?, theoretical calculations at the M06‐2X/aug‐cc‐pVDZ level were carried out.