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- Title
Reactivity of Liquid Ammonia Solutions of the Zintl Phase K<sub>12</sub>Sn<sub>17</sub> towards Mesitylcopper(I) and Phosphinegold(I) Chloride.
- Authors
Benda, Christian B.; Waibel, Markus; Köchner, Tobias; Fässler, Thomas F.
- Abstract
To gain more insight into the reactivity of intermetalloid clusters, the reactivity of the Zintl phase K12Sn17, which contains [Sn4]4− and [Sn9]4− cluster anions, was investigated. The reaction of K12Sn17 with gold(I) phosphine chloride yielded K7[(η2-Sn4)Au(η2-Sn4)](NH3)16 ( 1) and K17[(η2-Sn4)Au(η2-Sn4)]2(NH2)3(NH3)52 ( 2), which both contain the anion [(Sn4)Au(Sn4)]7− ( 1 a) that consists of two [Sn4]4− tetrahedra linked through a central gold atom. Anion 1 a represents the first binary AuSn polyanion. From this reaction, the solvate structure [K([2.2.2]crypt)]3K[Sn9](NH3)18 ( 3; [2.2.2]crypt=4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane) was also obtained. In the analogous reaction of mesitylcopper with K12Sn17 in the presence of [18]crown-6 in liquid ammonia, crystals of the composition [K([18]crown-6)]2[K([18]crown-6)(MesH)(NH3)][Cu@Sn9](thf) ( 4) were isolated ([18]crown-6=1,4,7,10,13,16-hexaoxacyclooctadiene, MesH=mesitylene, thf=tetrahydrofuran) and featured a [Cu@Sn9]3− cluster. A similar reaction with [2.2.2]crypt as a sequestering agent led to the formation of crystals of [K[2.2.2]crypt][MesCuMes] ( 5). The cocrystallization of mesitylene in 4 and the presence of [MesCuMes]− ( 5 a) in 5 provides strong evidence that the migration of a bare Cu atom into an Sn9 anion takes place through the release of a Mes− anion from mesitylcopper, which either migrates to another mesitylcopper to form 5 a or is subsequently protonated to give MesH.
- Subjects
LIQUID ammonia; AMMONIA synthesis; CHEMICAL reactions; POTASSIUM compounds; GOLD compound synthesis
- Publication
Chemistry - A European Journal, 2014, Vol 20, Issue 50, p16738
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.201404594