Zintl-Verbindungen mit Gold: M3AuSn4 mit M = K, Rb, Cs und M3AuPb4 mit M = Rb, Cs

Abstract

Silberfarbene, spröde Einkristalle der Verbindungen M3AuSn4 mit M = K, Rb, Cs und M3AuPb4 mit M = Rb, Cs wurden durch Umsetzungen von Alkalimetallaziden MN3 mit Goldschwamm und Zinn(Blei)‐pulver bei T = 923 K synthetisiert. Die Strukturen der isotypen Verbindungen (Raumgruppe Pmmn, Z = 2) wurden aus Röntgen‐Einkristall‐Diffraktometerdaten bestimmt: K3AuSn4: a = 6,938(1) Å, b = 12,544(1) Å, c = 6,523(1) Å; Rb3AuSn4: a = 7,147(3) Å, b = 13,081(4) Å, c = 6,558(1) Å; Cs3AuSn4: a = 7,459(1) Å, b = 13,707(3) Å, c = 6,597(1) Å; Rb3AuPb4: a = 7,078(1) Å, b = 13,220(2) Å, c = 6,787(1) Å; Cs3AuPb4: a = 7,333(1) Å, b = 13,821(2) Å, c = 6,828(1) Å. Die Zintl‐Verbindungen M3AuE(14)4 mit E(14) = Sn, Pb enthalten ∞1[AuE(14)4]‐Ketten, in denen P4‐analoge E(14)4‐Tetraeder über μ2‐verbrückende Goldatome mit verzerrt tetraedrischer E(14)‐Koordination verknüpft werden.

Reactivity of Liquid Ammonia Solutions of the Zintl Phase K12Sn17 towards Mesitylcopper(I) and Phosphinegold(I) Chloride

“…Anion 1 a is the first example of the AuSn intermetalloid cluster obtained from solution. The Au atom links two tetrahedral anions with mean AuSn bond lengths of 2.78 Å, which is close to the AuSn distances in the intermetallic compounds K 3 AuSn 4 (2.77 Å), K 23 Au 12 Sn 9 (2.67–2.73 Å), and NaAuSn (2.75 Å) 31. 32 The SnSn contacts between those Sn atoms involved in η 2 coordination (Sn1Sn2, Sn5Sn6; also labeled as Sn* in Table 1) are elongated (3.06 Å) relative to the Sn3Sn4 and Sn7Sn8 distances (2.94 Å), which have no contacts to the Au atom.…”

“…The [(η 2 ‐Sn 4 )Au(η 2 ‐Sn 4 )] 7− unit formed in ammonia solution is structurally related to the [Au(η 2 ‐Sn 4 )] 3− units that build infinite ${{{1\hfill \atop \infty \hfill}}}$ [Au(Sn 4 )] 3− chains in the ternary phases M 3 AuSn 4 (M=K, Rb, Cs). However, the solid‐state compounds are synthesized under rather harsh conditions through reactions of alkali‐metal azides with elemental gold and tin powder at 650 °C,31, 38 whereas compounds 1 and 2 can be obtained in solution at −70 °C.…”

Polyanionische Cluster und Netzwerke der frühen p-Metalle im Festkörper: jenseits der Zintl-Grenze

“…B. 1 I [Sn 4 Au 3À ]; [64,65] solche Verbindungen werden aber an dieser Stelle nicht näher diskutiert.…”

Reaction of Sn44− in liquid ammonia: the formation of Rb6[(η2-Sn4)Zn(η3-Sn4)]·5NH3

“…The coordination sphere of the anion is completed by 16 Rb + cations at Rb-Sn distances between 3.685(7) Å and 4.3798(3) Å (the discrepancy in the accuracy of the bond distances arises due to modeling some of the Rb positions with fractional occupancies) which interconnect the 1a anions to form a three dimensional network of cations and anions. The coordination sphere of the Rb atoms is saturated by two to three ammonia molecules at distances between 2.90(4) Å and 4.036 (7) Å.…”