Between Elemental Match and Mismatch: From K 12 Ge 3.5 Sb 6 to Salts of (Ge 2 Sb 2 ) 2- , (Ge 4 Sb 12 ) 4- , and (Ge 4 Sb 14 ) 4

• Published in: Angewandte Chemie International Edition 2022-10, Vol.61 (41), p.e202207232
• Main Authors: Beuthert, Katrin, Pan, Fuxing, Guggolz, Lukas, Wilson, Robert J, Hempelmann, Jan, Dronskowski, Richard, Dehnen, Stefanie
• Format: Article
• Language: English
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.202207232

The solid mixture "K GeSb" was shown to comprise single-crystalline K Ge Sb (1), a double salt of K [GeSb ] with carbonate-like [GeSb ] anions, and the metallic Zintl phase K Ge . 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: (Ge Sb ) (in 2), (Ge Sb ) (in 3), and in the presence of [AuMePPh ] also (Ge Sb ) (in 4). The anion in 2 represents a predicted, yet heretofore missing pseudo-tetrahedral anion. 4 comprises a cluster analogous to (Ge Bi ) and (Ga Bi ) , 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.