Characterization of Palladium(II) Azide and Crystal Structure of Bis(azido)bis(pyridine)palladium(II) and Tetramminepalladium Tetraazidopalladate(II)

Abstract

Palladium(II) azide (1) was synthesized by reaction of palladium nitrate and sodium azide. 1 was characterized by AAS, IR, and 14N‐NMR spectroscopy. Bis(azido)bis(pyridine)palladium(II) (2) and tetramminepalladium tetraazidopalladate(II) (3) were synthesized by a high‐yield reaction. Both were characterized by X‐ray structural analysis, IR, Raman, and NMR spectroscopy.

Experimental and Theoretical Characterization of Cationic, Neutral, and Anionic Binary Arsenic and Antimony Azide Species

“…However, the elemental analysis as well as the vibrational spectra of the solid indicate discrete Sb(N 3 ) 6 - anions. A similar phenomenon was observed for the palladium azide complex [Pd(NH 3 ) 4 ][Pd(N 3 ) 4 ] …”

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

“…In both compounds, the palladium atoms are located within a (distorted) tetragonal planar coordination sphere built up by the inner N i species of the azide ions. The Pd–N i distances within the complex anions ( 1 : d = 202.8(5) – 203.0(5) pm, d ave = 202.9 pm; 2 ‐ I : d = 202(2) – 204(2) pm, d ave = 203.3 pm; 2 ‐ II : d = 205(2) – 206(2) pm, d ave = 205.6 pm) are in the range also observed in other azidopalladate(II) compounds: for [Pd(NH 3 ) 4 ][Pd(N 3 ) 4 ] d = 205.6(2) pm 5; for [(PNP) 2 ][Pd(N 3 ) 4 ] d ave = 199.3 pm 9. In all complexes, the average angles Pd–N i –N c are nearly constant ( 1 : 123.0°; 2 ‐ I : 124°; 2 ‐ II : 123°; [Pd(NH 3 ) 4 ][Pd(N 3 ) 4 ]: 116.8 5; [(PNP) 2 ][Pd(N 3 ) 4 ]: 124.2° 9)).…”

“…Similar values of N–N–N angles down to 170° were found for azides, which are covalently bonded to a metal or an organic substituent 11. The [Pd(N 3 ) 4 ] 2– anions in ( 2 ) and Pd(NH 3 ) 4 ][Pd(N 3 ) 4 ] 5 are nearly planar, the dihedral angles between the azide group and the PdN 4 plane vary between 10.1° in 2 ‐ I , 4.1° in 2 ‐ II and 0° in [Pd(NH 3 ) 4 ][Pd(N 3 ) 4 ] 5. In contrast the [Pd(N 3 ) 4 ] 2– anions in 1 and [(PNP) 2 ][Pd(N 3 ) 4 ] 9 show significant torsion with dihedral angles of 29° and 23.8°, respectively.…”

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 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] …”

“…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).…”