Beuthert Katrin, Pan Fuxing, Guggolz Lukas, Wilson Robert J, Hempelmann Jan, Dronskowski Richard, Dehnen Stefanie
Fachbereich Chemie und Wissenschaftliches Zentrum für Materialwissenschaften, Philipps-Universität Marburg, Hans-Meerwein-Straße 4, 35043, Marburg, Germany.
Chair of Solid-State and Quantum Chemistry, Institute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1, 52056, Aachen, Germany.
Angew Chem Int Ed Engl. 2022 Oct 10;61(41):e202207232. doi: 10.1002/anie.202207232. Epub 2022 Jul 28.
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.
固体混合物“K GeSb”被证明由单晶K Ge Sb (1)、具有类碳酸根[GeSb ]阴离子的复盐K [GeSb ]以及金属性的津特耳相K Ge 组成。在穴状配体-222存在下，用乙二胺萃取1得到了几种新型二元津特耳阴离子的[K(穴状配体-222)]盐：(Ge Sb ) (存在于2中)、(Ge Sb ) (存在于3中)，并且在[AuMePPh ]存在时还得到了(Ge Sb ) (存在于4中)。2中的阴离子代表一种预测的、但迄今尚未发现的伪四面体阴离子。4包含一个类似于(Ge Bi ) 和(Ga Bi ) 的簇，因此是最富锑的二元p区阴离子之一。沿着簇生长的“死胡同”，3中前所未有的簇拓扑结构可被视为4中簇拓扑结构的缺陷版本。这些发现表明，锗和锑原子处于良好匹配和不匹配元素组合的边界。我们讨论了新化合物的合成、几何结构和电子结构。
