Synthesis, Crystal Structures, and Vibrational Spectra of Novel Azidopalladates of the Alkali Metals Cs₂[Pd(N₃)₄] and Rb₂[Pd(N₃)₄]·²/₃H₂O 

Abstract

The transparent dark orange title compounds are prepared by slow evaporation of aqueous solutions of K2PdCl4 and CsN3 or RbN3 (25 °C, 12—24 h; caution: the products are highly explosive).

The First Alkaline‐Earth Azidoaurate(III), Ba[Au(N3)4]2 ⋅ 4 H2O

“…Up to now, two different types of complex azidoaurate ions have been observed: in compounds with large cations, the azidoaurate ions show C 4h symmetry (e. g., [As-(C 6 H 5 ) 4 ][Au(N 3 ) 4 ] [18] ), whereas in all alkali metal azidoaurates the complex anion has C 2 symmetry. [17,33] Similar and further topologies are also observed in selected azidopalladates(II) [19,34,35] and azidoplatinates(II). [35] The coordination sphere of the barium cations (CN = 10) containing six azide groups of four different complex anions and four water molecules forms a highly irregular polyhedron (Figure 4).…”

“…Up to now, two different types of complex azidoaurate ions have been observed: in compounds with large cations, the azidoaurate ions show C 4 h symmetry (e. g., [As(C 6 H 5 ) 4 ][Au(N 3 ) 4 ] [18] ), whereas in all alkali metal azidoaurates the complex anion has C 2 symmetry [17,33] . Similar and further topologies are also observed in selected azidopalladates(II) [19,34,35] and azidoplatinates(II) [35] …”

“…The explosive nature of the azidoaurates has been shown to increase with decreasing cationic radius. [19] All azidoaurate(III) anions [Au(N 3 ) 4 ] À known up to now feature square-planar coordination of Au by N with azide species displaying a NÀ NÀ N bond angle of 172 � 3°and two different NÀ N bond lengths; [20] however, they show structural variety besides the ubiquitous "windmill".…”

“…The crystal structures and vibrational spectroscopic properties as well as topology and bonding of ternary azidoaurates(III) A [Au(N 3 ) 4 ] with monovalent metal ions ( A= K, Rb, Cs) [17] or complex cations ( A= [As(C 6 H 5 ) 4 ]) [18] have been investigated in more detail. The explosive nature of the azidoaurates has been shown to increase with decreasing cationic radius [19] . All azidoaurate(III) anions [Au(N 3 ) 4 ] − known up to now feature square‐planar coordination of Au by N with azide species displaying a N−N−N bond angle of 172±3° and two different N−N bond lengths; [20] however, they show structural variety besides the ubiquitous “windmill”.…”

Alkaline and alkaline earth metals

“…83 Cs 2 [Pd(N 3 ) 4 ] and Rb 2 [Pd(N 3 ) 4 ]Á2/3H 2 O have been synthesised by reaction of the respective binary alkali metal azides with K 2 PdCl 4 . 84 The crystal structure of sodium pyrosilicate (Na 6 Si 2 O 7 ) was determined. 85 A synthesis of the sodium salt of monosulfonated triphenylphosphane and its X-ray structure has been described.…”