[Ag12F(NPEt3)8]3+: Ein durch Fluorid gefüllter Metalla-Cryptand

Abstract

Professor Herbert W. Roesky zum 65. Geburtstag gewidmet Inhaltsu È bersicht. [Ag 12 F(NPEt 3 ) 8 ](SiF 6 ) 1,5 (1) wird durch Reaktion von Silber(I)-fluorid mit dem silylierten Phosphanimin Me 3 SiNPEt 3 in Acetonitril synthetisiert und als farblose, licht-und feuchtigkeitsempfindliche Kristalle isoliert, die eingelagertes Acetonitril im Vakuum abgeben. 1´2,4 CH 3 CN wird durch das IR-Spektrum und eine Kristallstrukturanalyse charakterisiert. Raumgruppe Pa 3, Z = 8, Gitterkonstante bei 153 K: a = 2734,8(1) pm, R = 0,059. Die Verbindung besteht aus [Ag 12 F(NPEt 3 ) 8 ] 3+ -Kationen der Symmetrie C 3 , [SiF 6 ] 2± -Gegenionen und eingelagerten Acetonitrilmoleku È len ohne bindende Wechselwirkungen. Im Kation besetzen die Silberatome die Kanten und die N-Atome der Phosphaniminato-Gruppen (NPEt 3 ± ) die Ecken eines nahezu idealen Wu È rfels. Das in das Wu È rfel-Geru È st eingelagerte Fluorid-Ion ist von den 12 Silberatomen mit nahezu gleichen Absta È nden von im Mittel 304,7 pm umgeben.Abstract. [Ag 12 F(NPEt 3 ) 8 ](SiF 6 ) 1,5 (1) was obtained from the reaction of silver(I) fluoride with the silylated phosphaneimine Me 3 SiNPEt 3 in acetonitrile. It forms colorless, lightand hydrolysis-sensitive crystals, which incorporate acetonitrile that is lost in vacuo. 1´2,4 CH 3 CN was characterized by its IR spectrum and by X-ray crystal structure analysis. Space group Pa 3, Z = 8, a = 2734.8(1) pm at 153 K, R = 0.059. The compound consists of cations [Ag 12 F(NPEt 3 ) 8 ] 3+ (point group C 3 ), SiF 6 2± counter-ions and acetonitrile mole-cules which show no interactions. In the cation the silver atoms are located on the edges of a nearly undistorted cube and the N atoms of the phosphoraneiminato groups (NPEt 3 ± ) occupy the vertices. A fluoride ion in the center of the cube has contacts of nearly similar length to the 12 silver atoms (mean distance 304.7 pm).

Untitled

“…242 Finally for N-donor complexes, another remarkable phosphineimine complex was obtained when AgF reacts with Me 3 SiNPEt 3 to give [Ag 12 F(NPEt 3 ) 8 ] + , which has N at the corners of a cube, Ag on the edges and F at the centre. 243 The controversial question of the existence of argentophilic interactions may be clarified by the assignment of an electronic transition in [Ag 2 (m-Cy 2 PCH 2 PCy 2 ) 2 ] 2+ salts as 4ds* to 5ps, using UV and resonance Raman spectroscopy on these luminescent salts. 244 The diphosphinoalkyne Ph 2 PCCPPh 2 (L) forms [Ag 2 L n ] 2+ (n = 1-3) depending on the stoichiometry of its reaction with Ag + .…”