![]() ![]() 3 However, there are still challenges that inorganic chemists are facing while seeking for novel Zintl cluster compositions, structures, and eventually properties.ĭuring the past two decades, it was shown that Zintl anions and their respective salts are excellent starting materials for the generation and isolation of compounds with heterometallic and intermetalloid cluster anions. One century after the discovery 1 and the first structural characterization 2 of Zintl anions, their chemistry has become remarkably diverse. The latter yields butterfly‐like structures that can be viewed as a new form of adaptable tridentate chelating ligands. Additionally, the results of an electrophilic attack by protons or trimethylsilyl groups or a nucleophilic attack by transition metal complex fragments are described. By analyzing the computational results, a concept was developed to predict which of the yet missing anions should be synthesizable and why. To contribute to a possible answer to this question, global minimum structures were calculated for all anions of the type (TrTt 3) 5−, (TrPn 3) 2−, and (Tt 2Pn 2) 2−, comprising elements of periods 3 to 6 (Tr: triel, Al⋅⋅⋅Tl Tt: tetrel, Si⋅⋅⋅Pb Pn: pnictogen, P⋅⋅⋅Bi). This brings up the question whether the other species are generally not achievable, or whether synthetic chemists just have not succeeded in their preparation so far. However, only ten of the theoretically possible 48 anions have been experimentally accessed to date as isolable salts. Binary pseudo‐tetrahedral Zintl anions composed of (semi)metal atoms of the p‐block elements have proven to be excellent starting materials for the synthesis of a variety of heterometallic and intermetalloid transition metal–main group metal cluster anions. ![]()
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