Darstellung, MOSSBAUER‐ und Schwingungsspektren der Azidokomplexe [SnCl₄(N₃)₂]²⁻ und [SnCl₄N₃]

Abstract

Die Umsetzung von SnCl4 mit Tetramethylammonium‐Azid in flüssigem SO2 führt je nach den angewandten Molverhältnissen zu [N(CH3)4]2[SnCl4(N3)2] (I) bzw. zu [N(CH3)4]2[SnCl4N3]2 (II). Mössbauer‐ und Schwingungsspektren belegen für (I) cis‐Stellung der Azidogruppen, während das mit [SbCl4N3]2 isoelektronische Anion von (II) einen zentrosymmetrischen Sn2N2‐Vierring enthält, der mittels der α‐N‐Atome der Azidogruppen zustande kommt.

Taming Tin(IV) Polyazides

“…Thed riving force for the azido-group transfer reaction involving TMSÀN 3 and fluorides arises primarily from the unusually high dissociation energy of covalent SiÀFb onds. [1a,c,d] Similart oo rganic azides, tin azides undergo N 2 elimination reactions with phosphines to yield phosphinimines, and cycloaddition reactions with alkynes and nitrilest oa fford triazoles and tetrazoles, [13] which so far precluded preparation/isolation of charge-neutral, nitrogenrich tin compounds such as Sn(N 3 ) 4 .W hilst tin polyazides of the types [Sn(N 3 ) 6 ] 2À , [14][15][16][17][18][19][20][21][22][23][24][25] [SnMe 2 (N 3 ) 4 ] 2À , [26] [SnF m (N 3 ) n ] 2À , m + n = 6, [27] SnCl 2 (N 3 ) 2[28] and [SnCl 4 (N 3 ) 2 ] 2À [29] have been known for some time, charge-neutral, nitrogen-rich tin complexes including Sn(N 3 ) 4 have not been reported. Early insight into the structure and bonding in poly(azido)stannate(IV) complexes was basedo nv ibrational, [15][16][17] Mçssbauer, [19,20] 14 NNMR [21] and 119 Sn NMR [30] spectroscopies.…”

“…[28] and [SnCl 4 (N 3 ) 2 ] 2À [29] have been known for some time, charge-neutral, nitrogen-rich tin complexes including Sn(N 3 ) 4 have not been reported. Early insight into the structure and bonding in poly(azido)stannate(IV) complexes was basedo nv ibrational, [15][16][17] Mçssbauer, [19,20] 14 NNMR [21] and 119 Sn NMR [30] spectroscopies.…”