Syntheses and Crystal Structures of Ammoniates with the Phenyl‐Substituted Polytin Anions Sn₂Ph$\rm{_{\bf 4}^{{\bf 2} - } }$, cyclo‐Sn₄Ph$\rm{_{\bf 4}^{{\bf 4} - } }$, and Sn₆Ph$\rm{_{{\bf 12}}^{{\bf 2} - } }$

Abstract

The reaction of diphenyltin dichloride with the binary Zintl phase K4Sn9 in the presence of excess lithium and 18‐crown‐6 in liquid ammonia led to the ammoniate [K(18‐crown‐6)(NH3)2]2Sn2Ph4 (1). The analogous reaction with K4Ge9 and potassium in the absence of further alkali metal ligands resulted in the compound [K2(NH3)12]Sn6Ph12 ⋅ 4 NH3 (3). Cs6[Sn4Ph4](NH2)2 ⋅ 8 NH3 (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 Sn2Ph$\rm{_4^{2 - } }$ anions consisting of Sn dumbbells with two Ph substituents at each Sn‐atom. Compound 2 contains cyclo‐Sn4Ph$\rm{_4^{4 - } }$ anions formed by a four‐membered tin ring in butterfly conformation with one Ph substituent at each Sn‐atom in an (all‐trans)‐configuration. Sn6Ph$\rm{_{12}^{2 - } }$ in 3 is a zig‐zag Sn6 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 [K2(NH3)12]2+ is observed. Compound 2 shows a complicated three‐dimensional network of CsSn interactions.

Diorganostannide Dianions (R2Sn2−) as Reaction Intermediates Revisited: In Situ 119Sn NMR Studies in Liquid Ammonia

“…More recently, synthesis of substituted diaryldimethylstannanes was proposed to proceed via the intermediate Me 2 Sn 2− , but also formation of the dimeric species (Me 2 Sn) 2 2− was anticipated, since the dimer (PhMe 2 Sn) 2 emerged among the reaction products or (18-crown-6)diammine potassium counterions.…”

The crystal structure of the first ether solvate of hexaphenyldistannane [(Ph3Sn)2• 2 THF]

“…In addition to the parent phenyl-substituted compound, crystal structures of the symmetric hexaaryldistannanes (p-Tol 3 Sn) 2 (Schneider-Koglin et al, 1991), (o-Tol 3 Sn) 2 (Schneider-Koglin et al, 1993), and [(C 6 F 5 ) 3 Sn] 2 (Bojan et al, 2010), and two co-crystalline compounds with included hexakis(2,6-diethylphenyl)distannane (Sita and Bickerstaff, 1989) and included {[o-(CH 2 NMe 2 )C 6 H 4 ] Ph 2 Sn} 2 (Turek et al, 2009), respectively, have been reported. The dianion Sn 2 Ph 4 2has been the subject of investigation in the context of phenyl-substituted Zintl anions of the heavier main-group elements (Scotti et al, 1997;Wiesler et al, 2006). To my knowledge, only for two solvates of (Ph 3 Sn) 2 singe-crystal X-ray structure determinations have so far been performed, i.e.…”