Schulz Axel, Villinger Alexander
Institut für Chemie, Universität Rostock, Albert-Einstein-Strasse 3a, 18059 Rostock (Germany); Abteilung Materialdesign, Leibniz-Institut für Katalyse e.V. an der Universität Rostock, Albert-Einstein-Strasse 29a, 18059 Rostock (Germany).
Chemistry. 2015 Feb 23;21(9):3649-63. doi: 10.1002/chem.201406023. Epub 2015 Jan 22.
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.
基于我们对二元元素-氮化合物的兴趣，我们在此报告了在一系列[Ph4P]+和[PNP]+（[PNP]+ = 双（三苯基膦）亚胺鎓）盐中合成并全面表征（熔点、红外/拉曼光谱、元素分析、14N/133Cd/199Hg核磁共振）三叠氮和四叠氮镉酸盐及汞酸盐阴离子E(N3)(2+n)（E = Cd，Hg；n = 1，2）的情况。研究了在二氯甲烷中的叠氮化物/氯化物交换以及多叠氮汞酸盐在乙腈溶液中形成四唑盐的过程。测定了所有新化合物以及用于比较的[Ph4P][Cd2(N3)5(H2O)]的单晶X射线结构。此外，首次展示了无水叠氮化镉(II)及其二甲基亚砜加合物的合成。为了更好地理解E(N3)2、E(N3)3和E(N3)4中的结构和键合，在M06-2X/aug-cc-pVDZ水平上进行了理论计算。
