Homoleptische Azidometallate

Abstract

Nicht explosiv sind Azidometallate, wenn im Festkörper genügend voluminöse Kationen vorhanden sind. Strukturuntersuchungen an Einkristallen solcher Verbindungen ergaben, dass das Azidion (siehe Bild) als kovalent gebundener, z. T. auch auf verschiedene Weisen verbrückender Ligand fungieren kann.

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

“…[1] Since this time many azides of the metals of the periodic Table have been synthesized. Azide chemistry is of recent interest, [2][3][4][5][6][7][8][9][10] for example Zn(N 3 ) 2 , [11] or Hg 2 (N 3 ) 2 , Hg(N 3 ) 2 , and the azide of Millon's base [12] have been synthesized and investigated in great detail, as previous works, several decades ago, could not characterize the compounds properly due to a lack of analytic tools. It is possible to obtain metal azides by using trimethylsilyl azide and the corresponding metal fluorides in order to achieve a complete fluoride-azide exchange.…”

Experimental Evidence for Linear Metal–Azido Coordination: The Binary Group 5 Azides [Nb(N3)5], [Ta(N3)5], [Nb(N3)6]−, and [Ta(N3)6]−, and 1:1 Acetonitrile Adducts [Nb(N3)5(CH3CN)] and [Ta(N3)5(CH3CN)]

“…

Dedicated to Professor Reint Eujen on the occasion of his 60th birthdayWhereas the existence of numerous binary transition-metalazido complexes has been reported, [1][2][3] no binary Group 5 azides are known. Only a limited number of partially azidosubstituted compounds of vanadium, niobium, and tantalum have previously been reported.

…”

“…When the volatile compounds (SO 2 , (CH 3 ) 3 SiF, and excess (CH 3 ) 3 SiN 3 ) were removed in a vacuum at À20 8C, pure, yellow, solid, room-temperature-stable pentaazido complexes were produced in quantitative yield. As expected for covalently bonded polyazido complexes, [22] they are shock-sensitive and can explode violently when touched with a metal spatula or by heating in the flame of a Bunsen burner.…”

“…Removal of the volatile compounds (CH 3 CN, (CH 3 ) 3 SiF, and excess (CH 3 ) 3 SiN 3 ) at À20 8C resulted in the isolation of the acetonitrile adducts of the pentaazido complexes.…”

Azide Chemistry – An Inorganic Perspective, Part I Metal ­Azides: Overview, General Trends and Recent Developments

“…New developments in this chemistry have been highlighted in several reviews 55,17,18,22. An important prerequisite for the isolation of such very nitrogen‐rich compounds is the use of particularly voluminous cations (PPh 4 + , AsPh 4 + ) which render the salts inexplosive 1,2,55a. Another large cation – bis(triphenylphosphin)iminium (bis(triphenylphosphoranylidene)ammonium) – repeatedly employed for the same reason occasionally forms unplanned as in the reaction of CuCl 2 with NaN 3 and triphenylphosphine to give (Ph 3 P=N=PPh 3 ) 2 [Cu(N 3 ) 4 ] 56.…”