Between Elemental Match and Mismatch: From K12Ge3.5Sb6 to Salts of (Ge2Sb2)2−, (Ge4Sb12)4−, and (Ge4Sb14)4−. (28th July 2022)

• Record Type: Journal Article
• Authors: Beuthert, Katrin; Pan, Fuxing; Guggolz, Lukas; Wilson, Robert J.; Hempelmann, Jan; Dronskowski, Richard; Dehnen, Stefanie
• Is Part Of: Angewandte Chemie. Volume 134:Number 41(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-07-28
• Subjects: Antimony -- DFT Calculations -- Germanium -- Intermetallic Cluster Formation -- Zintl Anions; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.202207232
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: The solid mixture "K2 GeSb" was shown to comprise single‐crystalline K12 Ge3.5 Sb6 (1 ), a double salt of K5 [GeSb3 ] with carbonate‐like [GeSb3 ] 5− anions, and the metallic Zintl phase K2 Ge1.5 . Extraction of 1 with ethane‐1, 2‐diamine in the presence of crypt‐222 afforded [K(crypt‐222)] + salts of several novel binary Zintl anions: (Ge2 Sb2 ) 2− (in 2 ), (Ge4 Sb12 ) 4− (in 3 ), and in the presence of [AuMePPh3 ] also (Ge4 Sb14 ) 4− (in 4 ). The anion in 2 represents a predicted, yet heretofore missing pseudo‐ tetrahedral anion. 4 comprises a cluster analogous to (Ge4 Bi14 ) 4− and (Ga2 Bi16 ) 4−, and thus one of the most Sb‐rich binary p‐block anions. The unprecedented cluster topology in 3 can be viewed as a defect‐version of the one in 4 upon following a "dead end" of cluster growth. The findings indicate that Ge and Sb atoms are at the border of a well‐matching and a mismatch elemental combination. We discuss the syntheses, the geometric structures, and the electronic structures of the new compounds. Abstract : Extraction of the intermetallic phase "K2 GeSb", actually comprising the new single‐crystalline compound K12 Ge3.5 Sb6, yields the long sought‐for binary anion (Ge2 Sb2 ) 2− and larger ones, (Ge4 Sb12 ) 4− and (Ge4 Sb14 ) 4−, which place the Ge/Sb combination at the border of elemental match and mismatch. The yet unknown diversity of these binary species predicts a rich follow‐up chemistry.