![]() 4 In 2012, we were able to add 4− in the compound crown-6] 4⋅12 NH 3 as part of the very short list of known anions with the shape of a monocapped nortricyclane-like cage. In the course of the reaction between crypt] 2⋅en and ZnPh 2, the binary anion 2− crystallized together with 4−. 7 In this manner, ternary anions like 3−, 4−, 4− ( Ln=La, Ce), and 4− were obtained. and used as a starting material for reactions with transition metal and lanthanide metal complexes. 3b This compound was reproduced by Dehnen et al. in the compound crypt] 2⋅en in 1982, as one of the first heteroatomic Zintl anions. 3, 4, 6 The 2− anion was initially synthesized by Corbett et al. ![]() 5įocusing on the tinbismuthides, this field is found to be scarcely investigated, as only three anions have been characterized to date, namely 2−, 2−, and 4−. In reactions of solutions of homoatomic polyanions with metal organic compounds or metal halogenides anions like 3− ( T=Ge, Sn), 3−, 3−, and 2− ( Pn=P, As) were obtained, in which the homoatomic and structural motives are conserved. 2, 3, 4 They could be characterized through X-ray diffraction and were primarily synthesized by using mixed precursor phases. Until now, among others, the anions 2−, 2− ( Pn=Sb, Bi), 4− ( x=1, 2), 2− ( E=In, Ga), 6−, 2− ( T=Sn, Pb), 2−, and 3− were obtained by the formal exchange of one or more atoms of the homoatomic cage. The type of element chosen for the substitution is a cardinal point in influencing properties such as the size and the solubility of the anions. 1 From these basic structures, heteroatomic clusters originate through partial substitution. Representative cluster anions that are present in a large number of the compounds known to date, and which can serve as building blocks for bigger clusters, are 4− and x− ( x=3, 4) for group 14 elements ( T=Si–Pb) or 3− and 3− for group 15 elements ( Pn=P–Bi). The insight into what kind of molecular structures may be built if only one element is employed forms part of our fundamental knowledge of main-group chemistry. The field of homoatomic polyanions of heavier main-group elements, the so-called Zintl anions, has been investigated since the beginning of modern chemistry.
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