Syntheses and Crystal Structures of Ammoniates with the Phenyl-Substituted Polytin Anions Sn2Ph, cyclo-Sn4Ph, and Sn6Ph

✍ Scribed by Katharina Wiesler; Christof Suchentrunk; Nikolaus Korber

• Publisher: John Wiley and Sons
• Year: 2006
• Tongue: German
• Weight: 527 KB
• Volume: 89
• Category: Article
• ISSN: 0018-019X
• DOI: 10.1002/hlca.200690113

✦ Synopsis

Abstract

The reaction of diphenyltin dichloride with the binary Zintl phase K~4~Sn~9~ in the presence of excess lithium and 18‐crown‐6 in liquid ammonia led to the ammoniate [K(18‐crown‐6)(NH~3~)~2~]~2~Sn~2~Ph~4~ (1). The analogous reaction with K~4~Ge~9~ and potassium in the absence of further alkali metal ligands resulted in the compound [K~2~(NH~3~)~12~]Sn~6~Ph~12~ ⋅ 4 NH~3~ (3). Cs~6~Sn~4~Ph~4~~2~ ⋅ 8 NH~3~ (2) was prepared by reacting diphenyltin dichloride with a surplus of caesium in liquid ammonia. The low‐temperature single‐crystal structure determinations show all compounds to contain phenyl‐substituted polyanions of tin. Compound 1 is built from Sn~2~Ph$\rm{_4^{2 - } }$ anions consisting of Sn dumbbells with two Ph substituents at each Sn‐atom. Compound 2 contains cyclo‐Sn~4~Ph$\rm{_4^{4 - } }$ anions formed by a four‐membered tin ring in butterfly conformation with one Ph substituent at each Sn‐atom in an (all‐trans)‐configuration. Sn~6~Ph$\rm{_{12}^{2 - } }$ in 3 is a zig‐zag Sn~6~ chain with two substituents at each of the Sn‐atoms. Both 1 and 3 have molecular counter cations, in the latter case the unprecedented dinuclear potassiumammine complex [K~2~(NH~3~)~12~]^2+^ is observed. Compound 2 shows a complicated three‐dimensional network of CsSn interactions.