Ammine Complexes of Na‐, Ag‐, Mn‐, and Zn‐Azides

Abstract

The synthesis of ammine metal azides is achieved through a simple route in liquid ammonia solution. Azides of silver, sodium, manganese, and zinc were obtained as ammine complexes from liquid ammonia and the solid compounds were characterized. The NH 3 solutions were investigated by means of NMR spectroscopy as well. The triamminesilver(I) azide as well as the unusual tetraamminesilver(I) 796and pentaamminesodium(I) azides are presented. The structures of the hexaamminemanganese(II) and hexaamminezinc(II) azides, which crystallize with four ammonia molecules of solvation, are elucidated. From these compounds the binary azides Mn(N 3 ) 2 and Zn(N 3 ) 2 were obtained by (careful) heating.

A Neutron Diffraction and Quantum‐Chemical Study of [Mn(ND3)6](N3)2

“…The azide anion shows N–N distances of 1.178(11) and 1.180(12) Å, its bond angle is linear with 178.7(10)°. Azide anions of compounds that also contain ammine complexes as cations show N–N distances from 1.1708(10) to 1.184(3) Å . The N–N distances agree with reported values for other azide anion containing compounds as well .…”

“…X‐ray diffraction on single crystals at room temperature of [Mn(NH 3 ) 6 ]Cl 2 showed a distance of 2.270(3) Å between the metal cation and the nitrogen atoms of the ammine ligands , . The Mn–N distances in [Mn(NH 3 ) 6 ](N 3 ) 2 · 4NH 3 have been reported in between 2.2668(7) and 2.3131(7) Å at 100 K . The compound does not crystallize isotypic to known hexaammine complexes of the halides, which may be due to the different hydrogen‐bond acceptor characteristics of the azide anion in comparison to a halide anion.…”

“…Sodium azide (Merck, zur Synthese) and silver nitrate (VWR, 99.9 %) were used as supplied without any purification. [Mn(ND 3 ) 6 ](N 3 ) 2 · 4ND 3 was obtained according to the literature and slowly decomposed under inert conditions at room temperature to circa 4 g of [Mn(ND 3 ) 6 ](N 3 ) 2 . The compound was filled into a vanadium cuvette, sealed, and investigated by powder neutron diffraction.…”

“…We recently described a new route to metal azides, which is based on the reaction of AgN 3 with various main‐group, transition, as well as rare‐earth metals , . One example was the reaction of manganese metal and we reported the formation of [Mn(NH 3 ) 6 ](N 3 ) 2 · 4NH 3 from the reaction at –36 °C, its conversion to Mn(N 3 ) 2 (NH 3 ) 2 at room temperature, and its transformation into the binary azide Mn(N 3 ) 2 . In order to elucidate the hydrogen bonding, the preparation of the deuterated compounds has been attempted as well.…”

[U(NH3)10]4+ Cations in Azide, Bromide, and Iodide Ammoniates and a Hydrolysis Product with an unprecedented [U(H2O)9]4+ Cation

“…Without the addition of AgClO 4 , UBr 3 is not oxidized in liquid ammonia, neither at −40 nor at +25 °C, and only the ammine complex compound [U(NH 3 ) 9 ]Br 3 is formed, [28,35] which will be reported in detail elsewhere. Therefore, Ag + cations act as an oxidant and that behavior has been used in the past for the syntheses of several compounds [40–42] …”