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, (14)N/(133)Cd/(199)Hg NMR) of tri- and tetraazido cadmate and mercurate anions E(N3)(2+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, theoretical calculations at the M06-2X/aug-cc-pVDZ level were carried out.