Zintl‐Verbindungen mit Gold und Germanium: M₃AuGe₄ mit M = K, Rb und Cs

Abstract

Schwarz‐glänzende, spröde Einkristalle von M3AuGe4 mit M = K, Rb, Cs wurden durch Umsetzung von Alkalimetallaziden MN3 mit Goldschwamm und Germaniumpulver bei T = 1120 K synthetisiert. Die Strukturen der Verbindungen (Raumgruppe Pmmn, Z = 2, K3AuGe4: a = 6, 655(1)Å, b = 11, 911(2)Å, c = 6, 081(1)Å; Rb3AuGe4: a = 6, 894(1)Å, b = 12, 421(1)Å, c = 6, 107(1)Å; Cs3AuGe4: a = 7, 179(1)Å, b = 12, 993(2)Å, c = 6, 112(2)Å) wurden aus Röntgen‐Einkristall‐Diffraktometerdaten bestimmt. Die elektrisch halbleitenden Verbindungen enthalten [AuGe4]‐Ketten, in denen P4‐analoge Ge4‐Tetraeder über μ2‐verbrückende Goldatome mit verzerrt tetraedrischer Koordination am Germaniumatom verknüpft werden.

Soluble Zintl Phases A14ZnGe16 (A = K, Rb) Featuring [(η3-Ge4)Zn(η2-Ge4)]6– and [Ge4]4– Clusters and the Isolation of [(MesCu)2(η3,η3-Ge4)]4–: The Missing Link in the Solution Chemistry of Tetrahedral Group 14 Element Zintl Clusters

“…A 6 CdPb 8 ( A = K, Rb) feature oligomeric [(Pb 4 )Cd(Pb 4 )Cd(Pb 4 )Cd(Pb 4 )] 10– chains (Figure c) and bare [Pb 4 ] 4– clusters. Linear polymeric chains ∞ 1 ([( E 4 )Au] 3– ) (Figure d) are found for the isotypic A 3 Au E 4 phases ( E = Ge and Sn with A = K, Rb, Cs; E = Pb with A = Rb, Cs), and analogous ∞ 1 ([(TlSn 3 )Au] 4– ) chains with tetrahedral cluster units of group 13 and group 14 elements occur in K 4 Au(TlSn 3 ) …”

“…(e–h) Species with ( E 9 ) cages. (a) [(Si 4 )(Cu-Mes) 2 ] 4– obtained by a reaction in liquid NH 3 ; (b) [(Ge 4 )Zn(Ge 4 )] 6– in Cs 6 ZnGe 8 ; (c) [(Pb 4 )Cd(Pb 4 )Cd(Pb 4 )Cd(Pb 4 )] 10– in K 6 CdPb 8 ; (d) ∞ 1 ([(Ge 4 )Au] 3– ) in K 3 AuGe 4 ; (e) [(Ge 9 )(Zn-Ph)] 3– ; (f) [(Ge 9 )Cu(Ge 9 )] 7– ; (g) [(Ge 9 )Hg(Ge 9 )Hg(Ge 9 )Hg(Ge 9 )] 10– ; (h) ∞ 1 ([(Ge 9 )Hg] 2– ) …”

“…A 6 CdPb 8 (A = K, Rb) 3 feature oligomeric [(Pb 4 )Cd(Pb 4 )Cd(Pb 4 )Cd(Pb 4 )] 10− chains (Figure 1c) and bare [Pb 4 ] 4− clusters. Linear polymeric chains ∞ 1 ([(E 4 )Au] 3− ) (Figure 1d) are found for the isotypic A 3 AuE 4 phases (E = Ge 4 and Sn 5 with A = K, Rb, Cs; E = Pb 5 with A = Rb, Cs), and analogous ∞ 1 ([(TlSn 3 )Au] 4− ) chains with tetrahedral cluster units of group 13 and group 14 elements occur in K 4 Au(TlSn 3 ). 6 Quite a number of ligand-free heterometallic clusters with nine-atom group 14 element cages (E 9 ) linked by group 11 or group 12 atoms have been obtained from reactions in solution using soluble Zintl phases K 4 E 9 , which contain [E 9 ] 4− anions, and metal−organic complexes or other coordination compounds of the d block elements; 7 examples are shown in Figure 1f−h.…”