Tkachenko Nikolay V, Boldyrev Alexander I
Department of Chemistry and Biochemistry , Utah State University , 0300 Old Main Hill , Logan , UT 84322-0300 , USA . Email:
Chem Sci. 2019 Apr 29;10(22):5761-5765. doi: 10.1039/c9sc00929a. eCollection 2019 Jun 14.
Nonagermanide clusters are widely used in inorganic synthesis and are actively studied by experimentalists and theoreticians. However, chemical bonding of such versatile species is still not completely understood. In our work we deciphered a bonding pattern for various experimentally obtained nonagermanide species. We localized the electron density the AdNDP algorithm for the model structures ([Ge], [Ge{P(NH)}], Cu[Ge{P(NH)}] and Cu(NHC)[Ge{P(NH)}]) and obtained a simple and chemically intuitive bonding pattern which can explain the variety of active sites and the existence of both and geometries for such clusters. Moreover, the [Ge] core is found to be a unique example of an inorganic Zintl cluster with multiple local σ-aromaticity.
九锗化物簇合物在无机合成中被广泛应用，实验人员和理论学家都对其进行了积极研究。然而，这类多功能物种的化学键合仍未被完全理解。在我们的工作中，我们解读了各种通过实验获得的九锗化物物种的键合模式。我们使用AdNDP算法对模型结构（[Ge]、[Ge{P(NH)}]、Cu[Ge{P(NH)}]和Cu(NHC)[Ge{P(NH)}]）的电子密度进行了定位，并获得了一种简单且具有化学直观性的键合模式，该模式可以解释此类簇合物的各种活性位点以及同时存在的η⁶和η⁵几何结构。此外，[Ge]核被发现是具有多个局部σ-芳香性的无机津特耳簇合物的一个独特例子。
