Eulenstein Armin R, Franzke Yannick J, Bügel Patrick, Massa Werner, Weigend Florian, Dehnen Stefanie
Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Str. 4, 35032, Marburg, Germany.
Wissenschaftliches Zentrum für Materialwissenschaften (WZMW), Philipps-Universität Marburg, Hans-Meerwein-Str. 6, 35032, Marburg, Germany.
Nat Commun. 2020 Oct 12;11(1):5122. doi: 10.1038/s41467-020-18799-6.
The access to molecules comprising direct Zn-Zn bonds has become very topical in recent years for various reasons. Low-valent organozinc compounds show remarkable reactivities, and larger Zn-Zn-bonded gas-phase species exhibit a very unusual coexistence of insulating and metallic properties. However, as Zn atoms do not show a high tendency to form clusters in condensed phases, synthetic approaches for generating purely inorganic metalloid Zn units under ambient conditions have been lacking so far. Here we show that the reaction of a highly reductive solid with the nominal composition KGaBi with ZnPh at room temperature yields the heterometallic cluster anion [KZnBi]. A 24-atom polymetallide ring embeds a metalloid {Zn} unit. Density functional theory calculations reveal multicenter bonding, an essentially zero-valent situation in the cluster center, and weak aromaticity. The heterometallic character, the notable electron-delocalization, and the uncommon nano-architecture points at a high potential for nano-heterocatalysis.
近年来，由于各种原因，获取包含直接锌-锌键的分子已成为一个热门话题。低价有机锌化合物表现出显著的反应活性，而较大的锌-锌键合气相物种呈现出绝缘和金属特性非常不寻常的共存现象。然而，由于锌原子在凝聚相中形成簇的倾向不高，到目前为止，在环境条件下生成纯无机类金属锌单元的合成方法一直缺乏。在此我们表明，在室温下，具有标称组成KGaBi的高还原性固体与ZnPh反应可生成异金属簇阴离子[KZnBi]。一个24原子的多金属环嵌入了一个类金属{Zn}单元。密度泛函理论计算揭示了多中心键合、簇中心基本为零价的情况以及弱芳香性。这种异金属特性、显著的电子离域以及不寻常的纳米结构表明其在纳米异相催化方面具有很高的潜力。
