Binary Polyazides of Zinc. Issue 36 (29th November 2016)

• Record Type: Journal Article
• Authors: Bresien, Jonas; Ott, Holger; Rosenstengel, Kati; Schulz, Axel; Thiele, Philipp; Villinger, Alexander
• Is Part Of: European journal of inorganic chemistry. Issue 36(2016)
• Page Start: 5594
• Page End: 5609
• Publication Date: 2016-11-29
• Subjects: Zinc -- Nitrogen -- Azides -- Polymers -- Polymorphism; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201601035
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract : Herein, we report on the synthesis, isolation, and comprehensive characterization (m.p., ATR‐IR/Raman, elemental analysis, 14 N NMR) of tetraazidozincate anions [Zn(N3 )4 ] 2– in a series of [Ph4 P] + and [PNP] + [PNP = bis(triphenylphosphine)iminium] salts. The phase polymorphism in [Ph4 P]2 [Zn(N3 )4 ] was investigated by temperature‐dependent Raman spectroscopy and by powder and single‐crystal X‐ray diffraction experiments, which indicate the occurrence of five room‐temperature‐stable, and one common high‐temperature phase, besides two polymorphs of the acetonitrile solvate [Ph4 P]2 [Zn(N3 )4 ]· MeCN. Moreover, the synthesis of zinc azide solvates Zn(N3 )2 · n solvent (solvent = DMSO, n = 1, 3/2, 3; MeCN, n = 2/3) is presented for the first time. Single‐crystal X‐ray structures of all new compounds were determined. For a better understanding of structure and bonding in E(N3 )2, [E(N3 )3 ] – and [E(N3 )4 ] 2– (E = Zn, Cd, Hg), theoretical calculations at the M06‐2X/aug‐cc‐pVDZ level were carried out. Abstract : A series of zinc azide solvates Zn(N3 )2 · n solvent (solvent = DMSO, n = 1, 3/2, 3; MeCN, n = 2/3), and tetraazidozincate anions [Zn(N3 )4 ] 2– as [Ph4 P] + and [PNP] + [PNP = bis(triphenylphosphine)iminium] salts were synthesized and comprehensively characterized. The X‐ray structures of all Zn(N3 )2 solvates, as well as six polymorphs of [Ph4 P]2 [Zn(N3 )4 ] could be determined for the first time.